This chapter aims to study the benefits that arise from the use of virtual reality technology and World Wide Web in the field of distance education, as well as to further explore the role of instructors and learners in such a network-centric mode of education. Within this framework, special emphasis is given on the design and development of web-based virtual learning environments so as to successfully fulfil their educational objectives. In particular, the chapter includes research on distance education on the Web and the role of virtual reality, as well as study on basic pedagogical methods focusing mainly on the efficient preparation, approach and presentation of the learning content. Moreover, specific designing rules are presented considering the hypermedia, virtual and educational nature of this kind of applications. Finally, an innovative virtual reality environment for distance education in medicine, which reproduces conditions of the real learning process and enhances learning through a real-time interactive simulator, is demonstrated.