The social learning network (SLN) constructed based on web 2.0 techniques demonstrates some unique characteristics comparing to traditional e-learning context based on 1.0 technique. In response to the new characteristics in SLN, we advance the theoretical understanding of user satisfaction by reconceptualising e-learning as a relational process among students. Based on that, we draw on network externalities and social capital theory to examine users’ satisfaction with social learning network. Considering that network externalities are involved in the process, we propose that two types of network externalities: direct network externality and indirect network externality moderate the relationship between social capital and user satisfaction. Theoretical, practical implications and future research are also discussed.