Introduction This study investigated entry-level dental students’ motives for studying dentistry at the University of Benghazi (UoB), Libya and career expectations among recent UoB graduates in an atypical context during the time of political unrest and identified factors associated with these motives.  Methods A cross-sectional survey was conducted in 2021–2022 for all entry-level dental students and recent dental graduates of UoB. A self-administered survey explored motives for studying dentistry, career expectation and associated factors. The questions were adopted from previous studies and pre-validated for use among Libyan students. Motives and career expectations were summarized, and their association with potential associated factors were assessed using chi-square test at p ≤ 0.05. Results One hundred eighty-four entry-level students and 156 recent graduates completed the surveys, response rates = 73.6% and 62.4%, respectively. The main motives to study dentistry were the desire to work in the healthcare field (183, 99.4%), interest in scientific knowledge (178, 96.7%) and because there were various dental specialities (168, 91.3%). The most common career expectations were setting up a business (107, 68.6%) and establishing a dental clinic (105, 67.3%). In addition, preference for working in the public sector (106, 67.9%), work-life balance (102, 65.4%) and financial gain (94, 60.3%) were the main factors associated with career expectations. Conclusion The main motive to join a dental school in Libya was academic interest. However, recent graduates showed more pragmatic expectations related to private practice ownership.