Distance learning (or eLearning) is considered one of the most rapidly evolving application areas of the Web that improves the traditional educational processes and methodologies of knowledge transfer. In recent years, there has been significant research and experimentation around the adaptation and personalization of the eLearning hypermedia that mainly concerns the timely delivery and adjustment of the content to user’s needs and perceptual characteristics. This chapter provides a new comprehensive approach of reconstructing eLearning content; by creating a user profile based on specific metrics of cognitive processing parameters (such as cognitive style, cognitive processing speed efficiency, working memory factors and affective parameters) that have specific impact into the information space. Such approach may be proved to be very useful in assisting and facilitating a student to better understand eLearning content and therefore increase his / her academic performance. In view of that, an adaptation and personalization Web-based environment has been developed. It is detached into a number of interrelated components, each one representing a stand alone Web system. An evaluation of the proposed environment is presented with the results being highly promising and encouraging for the continuation of our research, since there has been identified significant increase of learners’ academic performance when interacting with the personalized eLearning environment that is matched to their cognitive and affective parameters as well as visual working memory span capabilities.