The adoption of e-learning in response to COVID-19 is to ensure the continuous development of human capital through alternative means. Nevertheless, the success of e-learning systems depends much on the attitude of the users. This study developed and empirically tested a model to predict antecedents of students' actual usage of e-learning during the COVID-19 period. A synthesis of UTAUT 2, Self Determination Theory and Core Self-Evaluation Theory were employed to examine the behaviour of students using a sample of 1024. PLS-SEM was used to analysed the hypothesised paths in the model. The results revealed that (1) Personality is positively related to behavioural intention (2) Actual usage is positively influenced by motivational factors (3) Behavioural Intention positively mediates the relationship between motivational factors and actual use (4) motivational factors positively mediate the relationship between UTAUT 2 constructs and behavioural intention. The results will guide stakeholders in education, especially e-learning system designers to incorporate personality and motivational factors in the designing of e-learning systems in order to increase the acceptability of the system by students. This study is among the first few attempts to incorporate personality, motivation and UTAUT2 to examine e-learning users' behaviour, especially in Sub-Saharan Africa during the COVID-19 pandemic. This work presents a contemporary perspective of e-learning users' behaviour during the COVID-19 pandemic.