The purpose of this paper is to contribute to the literature on exploring the relationship between personality factors and student satisfaction with synchronous online academic learning. Currently, the relevant studies of abrupt adoption of the synchronous online teaching are scarce, leaving a gap in our understanding of what the relationship between personality and satisfaction with synchronous online academic learning is. A questionnaire-based survey was employed for the data collection. There were overall 555 usable questionnaires answered by students, at a Greek public university located in Athens during the lockdown period from March to April 2020. The size of the sample allows us to proceed with reliable statistical analyses and produce valid conclusions. The structure of the observed correlations was determined by the factor analysis method identifying the groups of variables that have a high correlation. Five factors retained (openness, conscientiousness, extraversion, agreeableness, neuroticism). The findings indicate that openness and conscientiousness have strong positive influence on student satisfaction while neuroticism has negative. Extraversion and agreeableness did not relate to the dependent variable. Future studies could test the validity of the findings reported here, in different contexts and inquire the potential existence of latent variables which may be confounding the relationships discussed in this paper. The present study’s findings may help college administrators design more effective academic programs in more efficient manners.