Volunteering might seem a rather odd tool to use in your job-seeking quest, but it does have its benefits.
When you volunteer for a particular cause, you will inevitably work with a host of different people, and these people are usually volunteers who are able and willing to help other volunteers with whatever needs they might have. While volunteering, you can demonstrate your abilities and commitment to other volunteers, who may refer you to prospective employers or clients. Volunteering is simply another way of networking, without going through any possible tricky situations whereby you try a bit too hard to gain attention from others.