But see, I think that for the first movie, they need to go with something drastically different, not another villain with a personal connection to Peter and a plot to take down Spider-man. The focus of the first film should be on establishing the world Peter lives in. Mysterio fills the role of the main villain not because he has some grand scheme or personal vendetta, but because he is the cities first true super-villain and no one knows how to handle this. So it's up to Spidey to save the day.
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Mysterio being the first super villain he faces, in of itself is not really compelling, you make Rhino the first villain and say he is compelling by being the first villain. You need more then that.
But that's not personal connection with Spidey though, Mysterio trying to make himself famous by driving Spidey mad is not a personal connection, he has no connect to Spidey's past and its not personal, he is using Spidey as a means to an end. Its more about sadism and ego on Mysterio's part then any true vendetta. Mysterio wanting to destroy Spidey because he wants to make a name for himself is worse in some ways then someone who thinks Spidey has wronged.
Again Mysterio is not going to be sympathetic, but doesn't get anything evil either, why I do care about him. He is just some generic bad guy, I have no reason to like or hate him, I need more of a reason to find him compelling then he happens to be a bad guy in a Spidey film, by that logic I should have found Electro or Venom compelling despite the fact they were both rather lame and not very compelling. If putting Mysterio in a film is just an excuse for giant set pieces, but he is just going to rob banks or something for two hours, count me out as wanting to see him as the main villain, that sounds like a gimmick rather then a character. If that is all Mysterio is going to do, what are the stakes of the film? If Spidey fails to stop Mysterio, what will Mysterio steal some marked, insured bills? Spidey failing to stop a bank robbery is not really the type of big stakes adventure you want to see on film.
Here is the problem with Spidey's rogues gallery, a lot of villains are more about gimmicks then characterization, so often writers write them as the same greedy one dimensional criminal, but with a different gimmick. Sometimes writers break some of these B-list villains out of that mold, but often they get lazy and they give B-list Spidey villains interchangeable personalities. I think a Mysterio who is obsessed with fame and uses psychological warfare, makes him different then say Shocker, who is motivated by greed and nothing else.
Movies have 3 acts structures with building action and a climax, what's Mysterio going do that would build towards a climax if he is not trying to destroy Spidey and provide him with a character arc?