My internship at a large company was most useful in cementing one idea in me: working at a large company is not for me. Things move so slowly you want to hang yourself, and you see the daily ritual of political jockeying in full force.
At the end of the internship the company offered me a nice position, but I was entirely uninterested. Instead I founded a company with a friend from school and have never looked back.
Money should not be a deciding factor at this point in your life. You will learn an order of magnitude more at a startup. If your goal is to spend your career creeping your way up the corporate ladder, or if you're unsure of your ability, work for the man. If you see entrepreneurship in your future, it's a no-brainer: go for the startup.