This study examined patterns of smoked substances (cigarettes and marijuana) among heterosexuals, gays, lesbians, and bisexuals based on data from the 2000 National Alcohol Survey, a population-based telephone survey of adults in the United States. We also examined the effect of bar patronage and sensation seeking/impulsivity (SSImp) on tobacco and marijuana use. Sexual orientation was defined as lesbian or gay self-identified, bisexual self-identified, heterosexual self-identified with same-sex partners in the past 5 years, and exclusively heterosexual (heterosexual self-identified, reporting no same-sex partners). Findings indicate that bisexual women and heterosexual women reporting same-sex partners had higher rates of cigarette smoking than exclusively heterosexual women. Bisexual women, lesbians, and heterosexual women with same-sex partners also used marijuana at significantly higher rates than exclusively heterosexual women. Marijuana use was significantly greater and tobacco use was elevated among gay men compared with heterosexual men. SSImp was associated with greater use of both of these substances across nearly all groups. Bar patronage and SSImp did not buffer the relationship between sexual identity and smoking either cigarettes or marijuana. These findings suggest that marijuana and tobacco use differ by sexual identity, particularly among women, and underscore the importance of developing prevention and treatment services that are appropriate for sexual minorities.