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Ask the good employees of Facebook, Google, AirBnb, etc. who joined those companies early on. The upside for the employees where the company IPO-ed is just insane.

Another reason might be the product/technology that the startup is working with that might be of interest to a good employee. Money is not everything.

I've asked them. To a one, they got lucky. None of them had an actual plan for how their contribution would lead to a multi-billion dollar exit.

I must second you here. Many times the stock options that you get at Google, or Facebook even today outperform all other forms of investment.

If you are talking just about $ then totally but there's more than just money. Big companies have bureaucracy, corporate politics, etc.

I'm working at one of those companies and I prefer the bureaucracy and real big data & machine learning over iterating on the web platform (Rails, Javascript, Angular...). With small companies it felt like I had to create features after features, but as there were not many users, I didn't have the same impact (number of users * $/user earned for the company)

Public companies can be a drag.