Of course being Spiderman is better in many ways than 100 million.
Say you choose the money, out of those 100M, how many do you have left after taxes?
Spiderman doesn't pay taxes, he broke. But the motherfucker is amongst the strongest heroes ever, nearly topping Hulk or Thor.
So, Spiderman clearly is the best choice precisely for the physical advantage over everybody.
Also, the motherfucker can dodge bullets thanks to spidersense, climb towers (and not fall from them) and buildings, bridges, trucks, any structure.
The guy might be broke but he's a genius too.
Now, in his black phase though... everything gets improved as Venom adds more physical strength, giving more advantages than being pure red broke man. It'd be too easy to steal money or other shit, nobody would stop you if you're the only Black Spiderman around.
So yeah, I'd choose to be Spiderman any time.
Pocahontas Jones can get my spiderweb too.