Volunteering is one of the quality education contents for college students. Studying the varied motivations of college students’ volunteering promotes the implementation of motivation education of college students’ volunteering, and exploring the influencing factors and relationships of college students’ volunteering behavior helps formulate appropriate systems and policies to promote college students’ volunteering activities. The motivations of volunteering behavior were analyzed using Exploratory Factor Analysis (EFA) to understand their classification and role, and the influencing factors were analyzed using Structural Equation Modeling (SEM) to study the occurrence path of volunteering behavior. The results of the study showed that utilitarian motivation has little influence on volunteering behavior, and volunteering ability and environment have a mediation effect on volunteering behavior, and volunteering environment has a significant moderation effect on volunteering ability and motivation.