It was discovered that the relation between certain personality traits and nicotine dependence differs among ethnicities and cultures; therefore, this study was conducted to determine which temperaments and personality traits are associated with smoking dependence in order to contribute to the development of effective and targeted interventions for smoking dependence within the Lebanese population. A cross-sectional study was carried out between March and April 2020 among a sample of Lebanese adults from all Lebanese governorates. The sample included (N = 501) divided as follows: 62 (12.4%) nonsmokers, 37 (7.4%) cigarette smokers, 266 (53.1%) waterpipe smokers, and 136 (27.1%) mixed smokers. Higher cooperativeness (B = − 0.03) was significantly associated with lower waterpipe dependence. High vs. low education level (B = − 0.97), female gender compared to males (B = − 1.07), higher cooperativeness (B = − 0.01), and higher self-transcendence (B = − 0.01) were significantly associated with lower cigarette dependence, whereas higher age (B = 0.03) was significantly associated with higher cigarette dependence. A multinomial regression analysis, taking the smoking group as the dependent variable, showed that higher harm avoidance (aOR = 0.97) and novelty seeking (aOR = 0.97) were significantly associated with lower cigarette smoking. A high level of education vs. a low one (aOR = 8.85) was significantly associated with higher cigarette smoking. Higher self-transcendence was significantly associated with lower mixed smoking. Being married vs. single (aOR = 2.46) was significantly associated with higher odds of being a mixed smoker, whereas female gender compared to males (aOR = 0.41) was significantly associated with lower odds of being a mixed smoker. These results are pivotal in understanding the relationship between personality and smoking dependence.