Students have long been associated to learn in groups in physical environments. As more and more digital libraries emerge, and libraries take a greater role in education together with academic institutions, there is a need to address digital libraries as learning environments. This chapter looks specifically at the process of learning between peers in a group and how digital libraries can lend themselves as a learning environment towards this purpose. Using a participatory process involving two groups of youths, observations were made to suggest design features for digital libraries used for electronic learning. This is a pilot study to investigate how youths collaborate with one another in a simulated learning environment. It is hoped that with a good understanding of the peer learning process, researchers can be assisted in future studies looking into digital libraries for educational purposes amongst learning groups.