Sure. Still, you might not be able to afford their salary and they migth have different job security expectations. Not all start-ups live in VC lala-land. Also

Sure. Still, you might not be able to afford their salary and they migth have different job security expectations. Not all start-ups live in VC lala-land. Also, experienced people usually don't jump for your entry level dev position. They are changing jobs to advance their career. In a start-up, you might not even have the positions they are looking for.