Studies showed that tobacco use and excessive alcohol consumption frequently occur, and both are significant causes of preventable morbidity and mortality. Data were collected as part of a national online study of the health of women in the fire service. Multinomial logistic regression was employed to determine factors associated with smoking and drinking characteristics. A total of 2330 women firefighters completed questions regarding tobacco and alcohol use; 3.2% (n = 75) were concurrent users, 0.9% (n = 22) were smokers only, 49.4% (n = 1150) were heavy drinkers only, and 46.5% (n = 1083) were low-risk users. Compared with those who neither smoked nor binge drank, concurrent users were more likely to be younger and live alone or not married. The findings also suggested that smokers, heavy drinkers, or those who were both were more likely to report symptoms of depression and PTSD and a history of physician diagnosis of anxiety disorder compared to low-risk users. Smoking rates are relatively low among women firefighters; however, mental health risks are prevalent, particularly for those who both smoked and drank heavily. Results can be potentially used to inform prevention and treatment research to better address the unique condition of this occupational group.