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Online social networks (OSNs) have gained popularity among users from all over the world during the past few years. And E-learning has made learning process quite convenient for users by using the networks. However, combing OSNs with E-learning is a new idea. And the role of OSNs in students' E-learning experiences is focused on in this paper. A study of Xiaonei which is one of the most popular online social network sites in China is conducted to explore the perception of students of OSNs based on the analysis of questionnaires. And the reasons that E-learning associating with OSNs will impact students' learning experiences are presented. And it is believed that online social networks can be effectively used in E-learning in the future.