Having worked predominantly in startups, we've almost always been cash-constrained in hiring. Some of the best hires I've found are highly motivated fresh grads or recent grads. I always look for the desire to prove themselves and take charge and full responsibility of a project; a majority of the times, money is secondary to these folks to the ability to make a difference and prove you're capable of completing something difficult. And ultimately, that's always something a startup can offer a young employee. That said, I've often had to teach them foundational things, but the desire to learn and get moving quickly outweighs any cons.
When I've been at big companies, it's all about experience and grey hair, and people become more motivated by money and low risk. I find many times, the quality of the average person at a big company is lower than the average startup fresh grad.