Elevated rates of cigarette smoking are observed prior to the onset of psychosis and remain stable early in the illness. Cannabis use frequently co-occurs with cigarette smoking and is independently associated with distinct clinical outcomes. However, past research has not controlled for cannabis use in cigarette smokers with first episode psychosis (FEP), limiting conclusions on the unique relationship of cigarette smoking to the demographic and clinical profiles of these patients. The present study therefore aimed to: (1) Determine the prevalence and patterns of cigarette smoking and its co-use with cannabis in FEP, and (2) Examine the demographic, clinical, cognitive, and functional characteristics associated with cigarette smoking status, after adjusting for frequency of cannabis use. Patients entering specialized treatment for FEP (N = 140) were divided into groups according to their current smoking status: 66 non-smokers (0 cigarettes/day), 47 light/moderate smokers (1–19 cigarettes/day; M = 9.81, SD = 3.93), and 27 heavy smokers (≥20 cigarettes/day; M = 26.39, SD = 6.31). The prevalence of cigarette smoking was 53% and smoking status was highly associated with frequency of cannabis use. After adjusting for cannabis use, significant between-group differences emerged. Heavy smokers were older at program entry and had a later age of onset of psychosis than light/moderate and non-smokers. Non-smokers had more education, better neurocognitive performance, and higher levels of functioning than light/moderate and heavy smokers. Prospective, longitudinal studies are needed to better understand the clinical significance of tobacco use and factors that contribute to the initiation and continuation of smoking behaviours in FEP.