This research analyzes college student's volunteers' participation flow experience, work satisfaction, and perceived value in the National-Games Empirical subjects were selected in the National Games 2011 at Chunghua, who served as volunteers at the site. Non-random sampling was employed to collect data, with 377 valid questionnaires obtained. Statistical analysis led us to conclude: 1.Volunteers was chiefly flow experience by "for me, it is pleasure to finish this will volunteers' task;" 2. In work satisfaction, volunteers saw participation in the tournament as a most satisfying volunteer service: "get along with will partner volunteers' harmoniously;" 3.There is powerful predicted on re-participation willingness is flow experience, work satisfaction, perceived value. Finally, suggestions for future studies and event planner are provided based on the results of this study.