The provision of Open Educational Resources (OER) means that learning horizons are no longer restricted by time and space. However, if the learning potential of OER is to be fully realised, educators and students must have the media literacy skills to select, use and produce information in a judicious and useful way. A consideration of the psychological dimensions of media literacy skills is crucial to maximise the learning opportunities offered by OER. Although learning platforms may be shifting to online content, the fundamental issues remain: How do we learn? How can learning be facilitated? These core psychological issues are key to the appropriate deployment and use of OER. The authors highlight how psychological theory and research has contributed to our understanding of technology-mediated interactions and the learning process, and consider how psychology can contribute to our understanding and application of OER as a learning facilitator. They discuss how advances in Web 2.0 technology may help maximise participation in learning and consider the potential psychological barriers and enablers to the uptake and use of OER.