Research on whether sexual orientation discrimination is associated with multiple tobacco product use among sexual minority (SM) adults is limited. Thus, we explored the associations between sexual orientation discrimination and exclusive, dual, and polyuse among a subset of SM adults (18+) (n = 3453) using the 2012-2013 National Epidemiologic Survey on Alcohol and Related Conditions-III. We evaluated six indicators of prior-to-past-year sexual orientation discrimination separately and as a summary scale and defined past-year exclusive, dual, and polyuse based on cigarette, electronic nicotine delivery systems, other combustible (cigars and traditional pipe), and smokeless tobacco products. Using multinomial logistic regression, we estimated adjusted associations between sexual orientation discrimination and exclusive, dual, and polyuse. Experiencing discrimination in public places, being called names, and being bullied, assaulted, or threatened were associated with dual use, while experiencing discrimination when obtaining health care or insurance and when receiving health care were associated with polyuse. Each one-unit increase in the sexual orientation discrimination summary scale was associated with 5% and 10% higher odds of dual (95% CI: 1.01-1.10) and polyuse (95% CI: 1.02-1.18), respectively. To conclude, we advise health professionals to consider the salience of discrimination against SM adults and how these experiences lead to dual/polyuse.