The rapid advancement of Internet and computer technology has not only influenced the way we live, but also the way we learn. Due to the implementation of e-learning in urban junior high schools in Taiwan, it has become essential to find out how external and internal factors affect junior high school students' online learning behavior, which consequently affects their learning outcome. The present study aims to propose a conceptual structural equation model to investigate the relationships among e-Learning system quality (eLSQ), technology readiness (TR), learning behavior (LB), and learning outcome (LO), and to demonstrate the direct and indirect effect of eLSQ and TR on LO from the perspectives of LB. Data collected from 10 urban junior high schools in Taiwan (N = 376) were analyzed using structural equation modeling. Results reveal that both eLSQ and TR have a direct and significant impact on LB. However, eLSQ and TR influence LO indirectly through LB. In addition, LB has a direct and positive significant influence on LO. Managerial implications are proposed and research limitations are discussed.