Previous studies analysing personality and cannabis use in adult samples suggest that cannabis users show significant higher levels of impulsivity, sensation seeking and schizotypy. However, there are few studies exploring this relationship in adolescence using psychobiological models of personality. Given the relevance of identifying individual differences that lead adolescents to early cannabis use to prevent future health problems, the present study aimed to explore the relationship between age, sex, personality and early cannabis use using a psychobiological model of personality in a sample of 415 students (51.8% boys) from 12 to 18 years. Chi² tests showed significant higher prevalence of cannabis use in boys and in the group aged 15–18 years. Multiple analysis of variance showed significant higher scores in psychoticism, sensation seeking and in all its subscales in cannabis users group, while an interaction with age was found for extraversion and neuroticism: cannabis users scored higher than non-users in the youngest group (12–14 years) but lower in the oldest group in both dimensions. Finally, regression analysis showed that narrower traits of sensation seeking (experience seeking and disinhibition) were the most associated to early cannabis use. Results are discussed in terms of early cannabis users’ personality profiles and in terms of the self-medication theory.