With over 800 million users worldwide, the global importance of Facebook as a social-networking platform is beyond doubt. This popularity, particularly among university-students, has encouraged research to explore ways in which social networking can be adapted into virtual learning environments. In particular, this study uses the think-aloud technique to explore university-students' use of and interaction with Facebook. Twenty-six Teesside University students who were also Facebook users took part in a think-aloud study. Seven major categories of experience emerged during the coding and categorisation process of the think-aloud data. Further analysis revealed that six fundamental psychological needs were each related to particular themes of user-experience. Overall, the results demonstrate that psychological needs are particular qualities of students' experience that are important in online social networking. Future research should investigate psychological needs in the context of virtual learning environments and ways in which these needs can be best supported for learning.