Introduction Substance use and mental health are robustly associated with smoking and poor cessation outcomes, but not often examined in combination with menthol cigarette smoking, which is also associated with lower quit rates. This study identified classes of Black and White menthol and non-menthol cigarette smokers based on demographics, alcohol, drug, and other tobacco use behaviors. Material and Methods Using screening data from two studies, latent class analysis (LCA) was conducted to classify n = 1177 menthol and non-menthol cigarette smokers on demographic characteristics, heavy smoking, alcohol and drug use, desire to quit smoking, other tobacco product use, and use of psychotropic medication. Results Three latent classes were identified that differentiated smokers on substance use, menthol cigarette smoking, and other tobacco use behavior. One class consisted primarily of young adults who used a wide array of other tobacco products, reported the highest prevalence of other drug use, and showed the lowest desire to quit smoking cigarettes in the next 6-months. Class 2 comprised primarily of Black male menthol smokers, all of whom used cigarillos in addition to cigarettes, and who displayed moderate drug use. The third class was categorized as primarily older cigarette smokers, who engaged in very little other tobacco use or drug use, but who were most likely to self-report being prescribed psychotropic medication. Conclusions LCA allowed for the identification of distinct classes of smokers based on factors related to poor cessation outcomes, including menthol use, that have not previously been examined in combination. Interventions should target specific groups of smokers, rather than take a “one size fits all” approach.