One of the major problems of using massive online open courses (MOOCs) commonly reported in the literature is the high dropout rate of students. Active participation in creating, sharing and managing content, simultaneous work on the same artefact, synchronous and asynchronous interaction and variety of functionalities that stimulate productivity in performing assignments are some of the benefits of employing social Web applications in MOOCs that have the potential to boost students’ motivation, thus addressing the aforementioned issue. Successful implementation of social Web applications in MOOCs is largely influenced by their acceptance by students. The aim of this paper is to examine the psychometric characteristics of the research framework which reflects the interplay of adoption determinants with respect to two representatives of social Web applications meant for collaborative work. An empirical study was conducted in which students of one Croatian higher education institution served as representative sample of users. Data were collected by means of the post-use questionnaire. The validity and reliability of the proposed research framework and associated hypotheses were examined by means of the partial least squares (PLS) structural equation modelling (SEM) technique. Implications for both researchers and practitioners are presented and discussed.