The Spanish educational system will require certain changes in order to achieve the Bologna objectives for the European Higher Education Area, including with new activities and roles for both students and teachers, who must assume new skills that will affect concepts and attitudes related to the teaching and learning processes. This chapter describes the authors’ experience in designing E-learning methodologies for the teaching of accountancy in the Business Administration Degree Course at the Polytechnic University of Valencia. The chapter’s methodology designed for teaching accounting, is based on PBL (Problem Based Learning), compiled with Internet based technologies. The authors analyze its use and evolution in two accounting subjects in the first and the fourth year of the degree. The conclusions obtained from the statistical treatment of the results show that there is a direct correlation between the use of an active E-learning model and obtaining satisfactory exam results in the subject.