In light of high unemployment and declining volunteer rates, this study examines the complex relationship between time, employment, and volunteering. Are unemployed people more likely to volunteer due to newfound time or to obtain some benefit? Alternatively, are the unemployed less likely to volunteer due to their loss of social ties or feelings of insecurity? A framework tying together four competing theories—opportunity cost, exchange, social ties, and attachment—into positive and negative influences is put forth and tested using pooled U.S. data from 2003 to 2013. The duration of unemployment emerges as a key factor, where volunteering decreases over time. Findings suggest organizations should recruit volunteers from untapped and under-represented groups, especially because the supply of volunteers is not endless. For example, unemployed volunteers devote more time but are less likely to receive an invitation to volunteer. Dedicated individuals may not volunteer simply because no one asks them.