The purpose of this study was to investigate the relationships among students' characteristics, flow experience and emotions towards physical education (PE). Quota sampling was applied to investigate this study purpose on students from 9 colleges nationwide. A total of 900 questionnaires were equally distributed to 9 colleges, 100 to each college, and 824 valid questionnaires were obtained. AMOS 17.0 was employed to process the analysis, and structural equation modeling was used to test the hypothesis fitness. Results indicated that students' characteristics including personal skills, challenging evaluation, as well as internal and external locus of control were affected positively to the flow experience towards physical education, and flow experience showed positive impact on positive emotions. In addition, students with internal or external locus of control had to have flow experience during physical education courses to result in positive emotions towards physical education. By recognizing the relationship on how flow experience is formed between physical education and students' emotions towards physical education, the PE teachers can better understand the demands from students with different characteristics. This study may further help teachers in setting up the new strategies to enhance students' emotions towards physical education and it is believed to be beneficial in the promotion of physical education.