For its advantages in being able to provide rapid and comprehensive access to knowledge, e-learning system has been widely adopted in education to improve learning processes. However, such IT-mediated processes involving both users and system are subject to changes. There exists adjustment in browsing behavior on user side and web structure refinement on system side. It would impose uncertainty and influence on learning quality and thus create a strong need for rapid adaptation between users and the e-learning system. Focusing upon knowledge organization in terms of web structure management, this study intends to find out an effective way to speed up the adaptation process. It consists of two stages. In the first stage, we would like to study the general adapting behaviors of e-learners, and analyze how they are affected by the web structure. Through analytical modeling, Knowledge Access Efficiency (KAE), which is capable of reflecting the quality of adaptation, is conceptualized mathematically. In the second stage, the dynamics of KAE during the whole adaptation process will be carefully investigated. It is hoped that this study can give us useful clues regarding knowledge organization of e-learning system, and by improving web structure management it can elicit better performance of elearners.