Depends on the startup and what stage it is. If it's a successful startup, then the CEO is sitting on a pile of stock that will likely be worth millions. If it's also a later stage startup, then likely he is making at least as much as his senior developers on top of that.
Either way, he's a much better bet if you want to be a millionaire's wife some day. Also, executives typically have expense accounts that afford them a very nice lifestyle _right now_, even if their salary isn't that high. You can be making a modest salary, but leading a jetset life on business expenses.
> Are there really very many VCs out there?
Yes there are. Here's just one random list of them: