This chapter aims at critically analyzing distance education and the interactions between ICT, teaching, and knowledge structures based on the contributions of psychopedagogy. The first section examines the innovations currently taking place in the field of psychopedagogy, in which the concept of the physical classroom is being replaced by that of the virtual classroom. The second and third sections analyze, respectively, the learning through ICT and the incorporation of the Web in the pedagogical practices, their possibilities, and limitations. A fourth segment regards the use of the Web by the youngsters and analyses the possible reasons for its great significance and use among youngsters. The conclusion of this chapter stresses the need to acknowledge the value of the interrelationship between the culture of physical presence and cyberculture in the teaching environment, as well as the need for teachers to change their mentality and to become effectively enabled to add ICT to their pedagogical practice.