Research has shown that individuals with greater public service motivation (PSM) values are more likely to work for government, because government jobs offer more public service opportunities; the question then arises of whether they are also drawn into other activities that offer service opportunities, such as participation in voluntary organizations. This study examined the volunteering behavior of government employees in different domains. Using the Americans’ Changing Lives survey, logistic regression models were estimated to examine the relationship between employment in the government sector and self-reported volunteering in five different types of organization. The results indicated that government employees engage in significantly more volunteering than their private-sector counterparts. When separate models were run for volunteering in each organization type, controlling for several other factors, the results showed that these initial big differences were driven primarily by their volunteering in two specific types of organization: Educational institutions and political groups.