Although there is a large volume of research on the relationship between social identity and volunteerism, little attention was given to national identity in volunteerism research. This study examined the role of national identity in motivating people to volunteer in the Chinese culture and its role in differentiating those who showed no interest in voluntary work (i.e. non-volunteers) from those who wanted to volunteer but did not (i.e. potential volunteers). Two hundred ninety-nine participants (age, M = 34.14 years) filled out a questionnaire on their demographics, experience of volunteering, intention to volunteer, volunteer motivations, and national identity. Results showed that a stronger national identity was associated with greater volunteer motivations. Mediation analyses further supported the positive indirect effect of national identity on intention to volunteer through strengthening volunteer motivations. Marital status was the only significant factor that differentiated current volunteers from potential volunteers. We concluded that citizens’ volunteer motivation increases with national identity, yet concrete measures to bring potential volunteers to actual volunteering need to be further explored. Copyright © 2012 John Wiley & Sons, Ltd.