Purpose: The purpose of the study is to determine the impact that the crucial determinants have on the behavioural intention (BI) of undergraduates to adopt Massive Open Online Courses (MOOCs), addressing two perspectives that are students' technical experience and psychosocial factors. Design/methodology/approach: This is a questionnaire study, and all the respondents are undergraduates in Barcelona, Spain. A total of 188 students are selected as survey subjects. Data collection applies the five-point Likert scale, and the collected information refers to demographic information and constructs related to the technology acceptance model (TAM) and theory of planned behaviour (TPB). Confirmatory factor analysis (CFA) and partial least square (PLS) are used to examine the measurement model's convergent and discriminant validity and test the hypotheses implementing the bootstrapping method. Findings: The results show perceived usefulness (PU) and perceived ease of use (PEOU) are influential in forming an attitude (ATT), and PU could directly impact BI significantly. Additionally, the mediating role of ATT in the relationships amongst PU, PEOU and BI are investigated. Besides, perceived behavioural control (PBC) is found a critical variable and significantly impacts BI, whereas subjective norms (SN) is not found statistically significant in explaining BI in this study. Originality/value: This study has confirmed that ATT has a positive mediation effect on PU, PEOU and BI. This study has also confirmed the validity and model fit of the incorporated model of TAM and TPB, which sufficiently accounts for the planned behavioural process of undergraduates to accept a MOOC and contributes to validating literature of the incorporated model of TAM and TPB. Besides, this study provides MOOCs managers with practical suggestions. First, ease-of-use interfaces should be designed and intensified. Second, more channels should be explored to satisfy students' needs. Third, managers should intensify the leverage of the systems and introduce the free trial period to new learners. Fourth, a bonus mechanism could be adopted to motivate students. Last, manager should intensify the construction of oral advertisements amongst students.