|Riolu & Lucario|
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Riolu is finally available early on in the wild. In fact, it's one of the first Pokemon you can catch, and it's an excellent one to go for at that. It evolves into the Fighting/Steel-type Lucario once it gains a level in the daytime after having a high enough happiness. Riolu's stats are alright for an unevolved Pokemon, particularly a baby Pokemon — it has quite high Attack and even decent Speed. Its defenses leave a lot to be desired, though. Once it evolves, not only does it gain that ever-useful Steel-type, giving it resistances to nearly everything, but it also gains amazing stats. Its Attack and Special Attack are both excellent. It can pull both off about equally, and both off very well, which is incredible. Its Speed is pretty darn good, too, allowing it to outspeed all but the speediest Pokemon out there. Its Defense and Special Defense, although being its weakest points, are still just around average, plus since it is resistant to so many things, it will take most hits with ease. It has either the Steadfast or Inner Focus abilities. Steadfast raises its Speed by one stage whenever it flinches, while Inner Focus prevents it from flinching. It just depends on if you'd rather take the flinch and get revenge for it or just forego it altogether. Personally, I prefer Steadfast, since Liepard and Fake Out are the main culprits of flinching (Lucario outspeeds most everything else), and regardless of if you flinch or not, Liepard (or whatever the Fake Out user is) is going to hit you anyway, so you might as well get a Speed boost from it. Either are nice, though, and help periodically throughout the game. Just remember to send Riolu or Lucario out when facing a Liepard, in case it wasn't already really obvious.
Riolu, sadly, does not start with very good moves. Quick Attack is the best you'll get early on, which is ok, but not at all sufficient against the Gym Leader on its own. Counter is picked up at level 6, which can be a risky gambit, hitting the foe for double the damage you received by any Physical-based attack, although it tends to be just a little too risky. Feint is learned at level 11, which has 30 power and hits through Protect, but that doesn't happen all that often. Force Palm at level 15 is the attack Riolu looks most forward to early on, giving it a medium strength Fighting-type attack hitting for 60 power and having a chance of paralysis. Unfortunately, it has only 10 PP, which will be a major bummer for your travels throughout Unova. You should definitely try to get your Lucario evolved by level 20 to 25 or so, and this can be done fairly easily by just riding back and forth on your Bicycle for fifteen minutes or so, then gaining a level. It's very worth it. It doesn't gain too many exciting moves in its 20's, though, so don't worry too much about the timing. As a Lucario, it gets Bone Rush at level 29, which strikes two to five times in a row for 25 power a pop, all as a Ground-type attack. It's a little risky, but it can hit pretty hard. Dig tends to be more reliable, though. Swords Dance at level 37 is great for raising Lucario's high Attack even further, particularly if you use a lot of Physical-based attacks. It's great when setting up for Gym Leader battles and other tough fights. Heal Pulse is learned at level 42, which heals the target Pokemon's HP by 50% of its maximum — useless in Single Battles, but helpful in Double or Triple Battles. Calm Mind is learned at level 47, which raises its Special Attack and Special Defense by one stage each and is rather nice. At level 51, it learns its signature move, Aura Sphere, which is a 90 power Special-based Fighting-type attack (20 PP, too!) that has perfect accuracy, like Swift. It gets Close Combat at level 55, which is a strong 120 power Physical-based Fighting-type attack that (sadly) lowers its Defense and Special Defense afterwards. Dragon Pulse is learned at level 60, hitting for a powerful 90 power Special-based Dragon-type attack, while ExtremeSpeed is learned at level 65, hitting as a much more powerful Quick Attack (although Lucario is generally fast enough anyway). Keep in mind that Lucario can also relearn Dark Pulse by exchanging a Heart Scale with the Reminder Girl in the Pokemon World Tournament, which is a good attack against the likes of Psychic- and Ghost-type Pokemon.
For TM moves, Riolu is capable of learning both Rock Smash and Work Up for very early-game moves, and both help it a bit. Rock Smash isn't as strong as Force Palm, but the extra PP helps, although it will quickly lose its potency. Dig and Rock Tomb are nice choices when you get to the desert, while Rock Slide and Psychic are nice options later on. Where Lucario really shines is Move Tutor moves. In Driftveil City, you can pick up either Ice Punch or ThunderPunch for 10 Red Shards each. Get 'em both if you want! Ice/Electric is a good combination. Dual Chop is also available for 6 Red Shards, but Ice-type attacks are even better against Dragon-types, so really go with that. Low Kick for 8 Red Shards is another possible option, but it isn't as good against lightweights, and there are plenty that Lucario will have to tear through. In Lentimas Town, it can learn Iron Tail for 6 Blue Shards, although its Fighting-type attacks cover the same things Steel-type attacks do, so you shouldn't bother. Zen Headbutt is a decent option for 8 Blue Shards and works better with Swords Dance than Psychic. It can learn Dragon Pulse early for 10 Blue Shards, but Ice Punch is usually sufficient enough (although Dragon Pulse's 90 power hits reliably hard against anything that isn't part-Steel-type and works well with Fighting-type attacks). When you get to Humilau City, a great move for Lucario is Drain Punch for 10 Yellow Shards. While pricy, it hits for a solid 75 power and, most importantly, heals Lucario's HP by half of the damage dealt. That will ensure its HP remains high through long training sessions and while exploring new areas. It's very helpful, although the 10 PP means it won't last forever, so Aura Sphere may be more desirable in the big picture. It depends on your style.
All things considered, Riolu is one of those Pokemon you should absolutely consider for your team if you are fortunate enough to find one. Make sure you evolve it as soon as possible, though. Seriously. Before you get your bike, if you don't mind running around like a lunatic for half an hour, that's a way to raise its happiness. Just make sure you do so in the daytime, because it won't evolve at night. But really, Lucario is just so amazingly good that it's hard to compare it to anything else. It is one of the best Pokemon out there and has no real flaws to it, other than lackluster Fighting-type moves until the later part of the game, which is what holds it back from its perfect rating. Trust me, it matters, but after that point, it is easily a perfect 5.