Most researches on the key themes of volunteer are illustrated by quantitative method of structured questionnaire. But the quantitative approaches can't offer macro and micro analytical perspectives about the participation process and motives which are embedded in volunteers. Beyond the surface and trifle of previous researches, this study takes qualitative method to ascribe the motives, beliefs, participation, process and devoted results of individual volunteer. Futhermore, this study extends to show the dynamic process of participation of volunteers and uses "grounded theory' to classify the data into categories to establish the participation types of volunteers. It also provides a new perspective for future researcher to know the volunteers. This study takes 28 volunteers of 5 volunteers' groups as sample and concludes 5 types of volunteer by "grounded theory" : (a) The type of hesitation. (b) The type of cautiousness. (c) The type of adaptation. (d) The type of coordination and direction. (e) The type of enthusiastic devotion. The incentive to service of the volunteers among the types of hesitation and discreetness is lower. They are hesitate and discreet to be engaged. The other three kinds of volunteers' participation types have greater motivations, activeness and willingness to help people. The also gain much sense of fulfillment, pleasure, and satisfaction. For the use of social work practical, field supervisors and works can take the five participation types to distinguish the new volunteers and understand the characteristics of volunteers as well as the problems they have. Social workers can use various kinds of social work methods to help each type of volunteers to stay in the institutions and reduce the attrition of volunteers. Besides, this five participation types can also help promote the management of human resources and the quality of service.