As long as students use Web 2.0 tools extensively for social purposes, there is an opportunity to improve students' engagement in Higher Education by using these tools for academic purposes under a Personal Learning Environment approach (PLE 2.0). The success of these attempts depends upon the reactions and acceptance of users towards e-learning using Web 2.0. This paper aims to analyse the factors (e-learning satisfaction and students' perceptions, among others) that determine the intention of use of a PLE 2.0 initiative. The study in addition analyses the moderating role of the Need for Cognition (NFC) in the model. The results indicate that the model proposed has a high explanatory power of the intention to use a PLE 2.0 and gives support to the moderating role of NFC. The study discusses how this analysis can help to improve course designs by teachers.