Lucario has a unique moveset, almost totally different from that of Mewtwo, whom he has replaced for this game, so you will need to practice to become a master with this Pokémon.
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Lucario is a solid fighter with almost all of his attacks in the exact middle of the weight classes (see Statistics for brief overview). But that's not exactly his main specialty: he has the unique ability to have his attack strength altered. His Aura, which are affected by his % and place, attacks increase in damage corresponding to his current place in the match and the % he has (max being 300% and last place; at this point, anyone over 70% can be KO'd).
But this doesn't mean that you'll be able to go into a fight when an opponent is one percent higher than you and you'll be able to KO him easy. It's the margin of distance between him and the 1st-place opponent. In other words, there's a big difference of his strength when he's, for example, 5% away than 50% away from the 1st-place opponent. Around every 8%-12% he's closer to 1st place, he loses a point of his attack power. It may not seem like much, but in the example, he could have an extra 6% in attack power, which is a lot for some of the powerful moves like Force Palm.
Although the Aura attacks are well known to be powerful, there's also another special ability he has that most of the other characters don't: the ability to latch onto walls while wall-jumping. If you let go of the control stick after jumping, he will stay on there for a long amount of time. This gives you three options: stay on the wall to wait for the time to jump in, immediately jump back in to continue fighting, or unleash an attack from where you are.
Note that since his attacks varies by how much he's damaged and what place he's in (for example, 150% and Last Place), all Aura-based attacks (such as Force Palm and Aura Sphere) will increase, making him extremely varied (as in the example, attacks are roughly twice as powerful than statistics). The statistics shown here are if he's at 0% and either tied or at 1st place.
Aura Storm: Lucario flies into the skies and fires a large beam of aura, which can be aimed in almost any direction below him. When initialized, this attack will begin by firing straight down (however you can change this by holding the control stick to either side). It can then be angled either to the left or right by holding the control stick in the desired direction (the direction of your enemy!). You can change the angle at any time.
The problem with this attack is that Lucario turns slowly — your enemy will easily outrun the attack and hover above the beam until it dissipates. However against a non-flying opponent this is more effective (for example, against Bowser, Gannondorf, or Ike). If you know which side your enemy will be on, make sure you tilt the beam before it fires so you can lift it even higher - however this still will not guarantee a hit because the attack can be air dodged.
In team battles you can use this attack to assist your teammate — either as a defensive mechanism (hide inside or on the other side of the beam), or offensive (knock them into the beam).