E-learning was crucial during the global lockdown. In this way, this article aims to propose and validate a holistic framework in which all the E-learning services are needed to ensure their effective implementation and use. To this end, an original 3S-T model, to measure E-learning success based on self-student assessment, was developed. This innovative model, which reinforces the existing theoretical framework of models, identifies a wide array of success predictors and relates them to various measures that help to reach success, including learning and academic achievements. The validation of the 3S-T model was carried out using the partial least squares structural regression equations modeling technique (PLS-SEM). In this analysis, four major constructors were identified as determinants of E-learning service performance, namely, the surrounding conditions, system characteristics, tutor’s development and student’s own performance. Although each of them is composed of several subcategories, finally, 15 indicators that estimate the fulfillment of these factors were defined and evaluated. The present study is strongly connected to the fourth goal of the Agenda established by the United Nations, which seeks Quality Education to ensure the sustainable development of countries.