Based on the data from students, parents and schools of the 2013 Survey of Student Digital Ability and e-Learning Opportunity from the Academia Sinica’s Survey Research Data Archive, this article constructed a hierarchical linear model to analyze how students’ e-learning opportunity is related to the multilevel influence effects of school- and parent-level covariates. Quantile regression was also used to study different covariate effects at different quantile levels of student e-learning opportunity. Results indicate that: (1) Digital Level Area is a very important influential factor for students’ e-learning opportunity due to the reason that schools in higher Digital Level Area have more digital resources, and students are likely to have more opportunity for access to and frequent use of e-learning; (2) the more IT equipment or IT literacy students have can greatly affect their possession of e-learning opportunity; (3) parents should pay special attention to problems of their children resulting from overuse of e-learning resources which could cause harm to their children both mentally and physically; moreover, schools should widely promote the awareness of personal information security to students; (4) in order to eliminate the digital divide caused by Digital Level Area, schools need to strengthen the integration of software and information technology into instruction as far as possible.