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Lucario is a favorite character of mine in Brawl, and I play as him fairly often. Here are some tips for those of you looking for a step up in your game.
Lucario has an ability called Aura. Put simply, the ability means that the more hits you take, the more powerful your own hits get! Take advantage of this by fighting aggressively at first, but play defensively once you take some significant damage.
One of the most useful moves in Lucario's arsenal is Double Team. When you are facing an aggressive enemy, back up a few steps, and use it as they come in close to hit you again. The next thing they know, you'll be slamming into them from behind!
Another move to use against aggressive opponents is Force Palm. At a distance, it sends out a short beam of energy. But when someone gets all up-in-your-face, use it to grab onto them and smack them with a pulse of power at point blank range!
When you need to take the fight up close, remember not to go too close. All of Lucario's basic moves do not need to have a limb connect to do damage. As a general rule, try to stay the same distance away as the width of Lucario's stance from your opponent when you attack. That way you will be just out of reach of them, but still able to knock them back.
Remember this tip when you get to use Lucario's Final Smash, Aura Storm: You can start to aim before shooting the beam! Tilting towards your target before shooting gives you a better chance to hit.
Finally, always remember to take every chance you get to charge your Aura Sphere! Whenever the enemy is a good distance away from you, take a second to charge it up. And remember, this is the move which is affected the most of all by the Aura ability. At 0% damage, it won't get very large, but at around 150%, it really packs a wallop!