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No. A nonexempt employee must be paid for all hours worked and generally may not "volunteer" to work for their employer without pay.
The Division of Labor Standards Enforcement takes the position that "volunteers" are those persons who donate their time to religious, charitable or similar nonprofit organizations for public service, religious or humanitarian purposes. If a person meets these requirements, they are not considered an employee for wage-and-hour purposes.
In general, most employees who offer to work without pay do not qualify as volunteers. For example, if an employee offered to work extra hours without pay to help meet a deadline, they would not be considered a volunteer and would have to be paid for all hours worked — including any applicable overtime. On the other hand, the same employee could offer to volunteer time for a blood drive, food drive or other similar type of charitable or philanthropic activity in the workplace and would be considered a volunteer.
Note: A person who works without compensation for the purpose of gaining experience in an occupation is an employee, not a volunteer.