Nowadays, the growth rate of social websites is not only impressive, but also turns up increasingly in the researches of the domestic and foreign research institutions. Both found that the use population, the frequent uses and others are rose substantially in social website. At the same time, social website strengthened the relationships of users and a gain of the contentment and happiness in the interactions. This pleasure is one of the factors to produce the flow experiences. Thus, the significance and predictive of flow experiences are motivation of this research. In addition, there is a deficiency of relevant researches in the researches of the relationships between the flow experiences of users and personality. Therefore, the main purpose of this study is to find out the relationships of the flow experiences between the users when using the social website and other effects of respective personality. Results show that, there are connections between the eight features of flow experiences and levels of involvement. In addition, the best explanations are the arousal, interactive, transformation of time, and the skills between each factor. The results of the validation of personality showed that only interference is the openness characteristic. Unexpectedly, found the other characteristics of personality regarding to the eight features of the flow experiences. By this study, confirmed that the characteristics of flow experiences do affect the involvement of users. While, the personality do influent the flow of the experiences and level of involvement bring the different effects. Moreover, base on these discoveries, users are recommended to update new programs and the interactive and respondent functions to attract more users and to promote the levels of usage.