I spent my summers doing small-scale freelance projects on sites like rentacoder.com and scriptlance.com. It gave me some extra money while I did something I enjoyed.
It gave me a lot of exposure to different technologies I didn't really think of trying myself, and it gave me actual motivation to follow through with learning them (you know, since someone is paying you). Have to stick to easy stuff though, since if you aren't concrete on the technologies you can get in over your head real quick. I have had luck telling buyers "Im a college student, and i'm eager to learn this" - some are very cool with that, and some way absolutely not, which is understandable.
It also gives you the experience of working with a large variety of people, and builds your ability to communicate technically when you aren't face to face with someone.
Lastly, each of these sites allows the people you work with to leave feedback about you and rate your performance. A list of stellar reviews on freelancing sites to show potential employers not only showcases your motivation, but also the fact that you can work with people.