Collaborative Filtering has been widely used in Recommender Systems helping customers of e-shops to find out items matching their requirements in huge or complex search spaces. There exist many commercial applications that show the utility of these systems, especially in e-commerce whose features and good performance obtained has driven us to consider their application in a specific domain as Academic Orientation, in order to support students’ decisions through their academic journey. We propose the use of the ideas behind the Collaborative Recommender Systems to develop a Web-based Decision Support System (Web-DSS) for Academic Orientation that analyze the students’ skills, attitudes, preferences, etc., and then compute relevant information to support their decisions concerning their academic future. Furthermore, we shall study the performance of such techniques in Academic Orientation by using a dataset gathered from various Secondary and High Schools in Spain. OrieB, a web-DSS for academic orientation is then presented.