Smoking cigarettes and low socioeconomic status (SES) are both related to impaired cognition. However, it is unknown whether people of lower SES, who comprise most tobacco smokers worldwide, are more susceptible to cognitive impairment associated with smoking. In this non-randomized, cross-sectional study we investigated the effects of cigarette smoking, SES and their interaction on dissociable executive or “cool” and “hot” measures of behavioural self-regulation. Participants (n = 80) were selected among young physically and mentally healthy smokers and non-smokers who had graduated high school and were from different SES backgrounds. Cool self-regulation was measured by executive function tasks that tap inhibition, updating, shifting, dual tasking, planning, access to long-term memory (semantic fluency), and working memory capacity. Hot measures assessed self-reported impulsivity, delay discounting and risk taking. Exposure to tobacco (cotinine, exhaled carbon monoxide, tobacco dependence, cigarette consumption) was assessed to determine to what extent it mediated the cognitive effects of smoking. Nicotine abstinence and its acute effects were controlled, as were sex, age, schooling, and psychiatric symptoms despite the fact that smokers and non-smokers were selected as being as similar as possible in these demographic characteristics. Lower SES (less years of parental schooling) was associated with worse performance on tasks that measured all cool domains except dual tasking and fluency, while smoking status was related to impaired delayed discounting and impulsivity (hot domains), effects that were not mediated by tobacco exposure. Smoking and SES, however, did not interact. In short, impaired performance in measures of most cool skills was associated with SES irrespective of smoking status; in contrast, regardless of SES, smokers showed specific impairment in hot self-regulation domains (more difficulty resisting immediate temptations and weighing future consequences of actions). Possible explanations for the lack of mediation of tobacco exposure on hot skills of smokers are discussed.