The purpose of this study is to identify the role personality plays in students’ satisfaction with synchronous online academic learning (SOAL), especially during the COVID-19 pandemic. According to the literature, overall students’ satisfaction with SOAL depends on a number of factors including the quality of SOAL, the quality of the course design, the responsiveness of the instructors, the institutional preparedness, the infrastructure available, and the fairness of the evaluation system. To fully explore the students’ satisfaction with SOAL it is important to examine another important aspect that relates to students’ personalities. For the purpose of this research, an online questionnaire was delivered to undergraduate business students of a public university in Athens during the first spring lockdown period of 2020. The findings of the study indicate that openness and conscientiousness, two of the big five personality traits, present a positive relationship with overall satisfaction with SOAL (Sahinidis & Tsaknis, 2021). They also revealed that students with higher levels of overall satisfaction with SOAL present higher levels of openness, conscientiousness, extraversion, and agreeableness but lower levels of neuroticism. This research study will make a remarkable contribution to the literature regarding the relationship between personality and students’ satisfaction with SOAL.