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If you performed volunteer work for a recognized charity you can enter your expenses for mileage, supplies you purchased, etc. You cannot deduct anything for your time, expertise or talent. Enter your volunteer expenses in the section for charitable donations.
If you are doing volunteer work for a qualified charity (one recognized by the IRS, which includes all the well-known charities as well as churches, etc.), then you can deduct on Schedule A as a charitable contribution any actual expenses you incurred in doing the work. This can include mileage, etc.
What you cannot do is get a deduction for your time.
Take a look at IRS Pub 526 at the top of page 5.
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