E-learning in higher education can be of great relevance in effective life-long learning education for sustainable development in a population of students who are simultaneously full time employees. The aim of this research was to assess the Education of Sustainable Development effectiveness through e-learning in higher education in a case study. The expectations and experience of students who enrolled in more than one programme in environmental and/or sustainability science (bachelor, master, and doctorate), offered by Universidade Aberta, the Portuguese Distance Learning University, were analysed. The six dimensions analysed were: general expectations; learning quality; teaching resources, pedagogical tools and evaluation; acquired competences in education for sustainable development; satisfaction and interactions; and reasons to pursue enrolment in a new programme at Universidade Aberta. Data was collected using semi-structured qualitative interviews. The results showed that the surveyed students felt that they attained a high level of motivation and satisfaction, and had reached an effective learning outcome of knowledge, competences, values, attitudes and behaviour in environment and/or sustainability sciences. For these reasons they were motivated to return to Universidade Aberta and enrol for further training in the sustainability area. These results are built upon previous work developed by the authors, and allow us to conclude that formal e-learning programmes can provide an effective alternative to face-to-face training, allowing students to pursue their studies, in a flexible, collaborative and interactive way, whilst holding down full time jobs. In this way, Education for Sustainable Development in an e-learning regime can contribute to, and have a role in, the transition to sustainable societal patterns