Putting your volunteer work on your resume can demonstrate that you are active and passionate outside of work. It shows some personality in a document that can often be impersonal. I would put this information in a brief and succinct bullet in the last section ("Additional Experience/Other Experience") of my resume.
Volunteer work can also help bolster a resume that is lacking in work experience, especially for recent graduates. When I was looking for my first job right out of college last year, I had listed the following volunteer work under work experience in my resume:
P.R.O.V.I.D.E.S. (Global Service Organization) , Ann Arbor, MI
Treasurer (May 2007-Present), Education & Social Committee Leader (May 2006-May 2007)
• Successfully led a 130+ member organization committed to executing impacting philanthropy, campus fundraisers, and campus awareness events aimed at alleviating global hunger and poverty.
• Effectively compiled grant and appeal requests for a cumulative funding of more than $5500 over the course of a year to surpass PROVIDES' budget restraints.
• Managed operations budget of $1500, prepared Excel sheets tracking financial state of entire organization, and coordinated the flow of disbursements.
• Increased fundraising donations to $700 per month and doubled membership through creative marketing strategies and successful fundraisers.
U OF M PSYCHOLOGY DEPARTMENT, Ann Arbor, MI
Academic Peer Adviser
• Planned and organized psychology-related academic events and forums about careers and higher education in psychology and successfully attracted over 50 students to attend each event.
• Guided over 200 students to solving their academic problems and helped them design academic and career plans on a one-on-one basis.
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Depending on the type of charity work performed it is possible it could help your resume. Typically a applicant for any jobs position though, is judged on prior work experience and credentials.