This paper discusses the relationship between corporate volunteering and civic engagement outside the workplace in Russia, proceeding from a mixed-method approach. The quantitative findings are based on a comparison between employees in 37 Russian companies who participated in corporate volunteering (N = 399) and those who did not (N = 402). Using binary logistic regression analysis, we demonstrate that employee participation in corporate volunteering is positively related to four forms of civic engagement outside the workplace: informal volunteering, formal volunteering, formal monetary donation, and informal monetary donation. In addition, we draw on information obtained from interviews with 10 corporate volunteers, as well as with all 37 company corporate volunteering managers, to develop a general explanation for why corporate volunteering might lead to civic engagement. We identify three primary explanations. First, trust in companies can be converted into increased trust in social institutions. Second, corporate volunteering can expose employees to other realities, thereby leading them to rethink their priorities. Third, corporate volunteering socializes employees to volunteering, thus making them more likely to incorporate volunteering into their personal repertoires of activities. Corporate volunteering appears to be an effective mechanism for stimulating civic engagement and volunteering infrastructure in post-communist countries.