Save all of the people on the train and complete the other levels until you reach the level where he recreates his machine. To complete this level you must destroy all of the power generators. To do this, follow the cord that is streaked with orange (or yellow) and black to get to the generators. Simply kick them to destroy them. His shield will then go away and you must take out all of his legs; however, be careful. Then to defeat him, keep punching and kicking away.
You first need to know which hologram is him. To do that, look at the faces behind all of the holograms and the one that is smiling will have the real Mysterio directly in front of it. Do not touch him while the three fireballs are orbiting his head. When he tries to shoot you and no longer has them orbiting his head, go in and hit him. When the fireballs return, back off. Repeat this. Note: Do not forget about the other holograms; they are just as powerful.
To defeat Rhino, simly jump. While you are in the air, press L and wait for him to run into the wall. Then get some combos on him. When he runs into the next room, do the same. Run around the poles when he gets the big pipe.
To defeat Shocker, let Rhino knock down the platform he is standing on (see the "Defeating Rhino" hint). Then lock in on him with the Spidey target and either blind him or hold L and press Triangle. Keep doing that and try not to die.
Stay in the construction area on top of the building and remain in between the two buildings so that Vulture cannot get to you. After some time his health will get down to green. He will land, and this is when you can attack him. Do it quickly; you only get five to ten seconds to punch him.