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If you are looking to transition into another field, volunteering can be a fantastic way to go about it. When you volunteer for a particular organization, there are often opportunities to move into a paying position; if not at that particular place, then somewhere else in the field. You can gain valuable job experience and receive training as well. Plus, it looks great on a resume!
If you have an interest in a particular field, look to see what opportunities there are to volunteer in the area that you are hoping to find employment. For example, if you are a freelance copywriter, ask if the organization needs work done for a new website or newsletter. Some places may require that you commit to a regular number of hours, whereas others may be happy to have you fill in on an as-needed basis. Check to see what the facility is looking for before you jump in. You'll want to make sure you have the time to do a good job without adding too much to your schedule.
Volunteering has the added benefit of serving as a "trial run," so that you can experience a work environment without doing the job full time. This can give you the chance to see if you would really enjoy a full-time position--before you sign on for the ride. If you decide against it, you'll still have some volunteer experience to list on a resume, and if it works out for you, you'll have a new job!