Smoking is a major public health issue which has been shown to increase an individual’s risk of disease and premature mortality. Understanding the factors that are associated with smoking may assist in the development of strategies to change smoking behaviour. The aim of the present study was to investigate the relationships between psychosocial factors and smoking behaviour in a young adult population. The participants were 204 participants from the University of Edinburgh. Information on socio-demographic factors, smoking habits and psychosocial factors including personality traits, emotional intelligence and perceived stress were collected using a self-administered questionnaire. Current smokers reported poorer perceived health than ex smokers and never smokers (p = 0.001). Male ex-smokers had lower emotional stability scores than current smokers and never smokers (p = 0.04). Females who had ever smoked (ex and current smokers) had higher Extraversion scores than females who had never smoked (p = 0.04). In multiple logistic regression analyses, Extraversion was found to be an independent predictor of smoking initiation, accounting for 3% of the variance. Furthermore, collectively age in years, average monthly income and social class predicted 30% of the variance in smoking consumption. In conclusion, individuals with higher extraversion scores were more likely to take up smoking at a younger age and socioeconomic factors may be important in maintaining smoking behaviour. These findings have implications for public health initiatives aimed at smoking prevention and cessation.