ObjectiveWe aimed to characterise self-reported military and occupational exposures including Agent Orange, chemical/biological warfare agents, solvents, fuels, pesticides, metals and burn pits among Veterans in the Department of Veterans Affairs Million Veteran Program (MVP).MethodsMVP is an ongoing longitudinal cohort and mega-biobank of over one million US Veterans. Over 500 000 MVP participants reported military exposures on the baseline survey, and over 300 000 reported occupational exposures on the lifestyle survey. We determined frequencies of selected self-reported occupational exposures by service era, specific deployment operation (1990–1991 Gulf War, Operation Enduring Freedom/Operation Iraqi Freedom (OEF/OIF)), service in a combat zone and occupational categories. We also explored differences in self-reported exposures by sex and race.ResultsAgent Orange exposure was mainly reported by Vietnam-era Veterans. Gulf War and OEF/OIF Veterans deployed to a combat zone were more likely to report exposures to burn pits, chemical/biological weapons, anthrax vaccination and pyridostigmine bromide pill intake as compared with non-combat deployers and those not deployed. Occupational categories related to combat (infantry, combat engineer and helicopter pilot) often had the highest percentages of self-reported exposures, whereas those in healthcare-related occupations (dentists, physicians and occupational therapists) tended to report exposures much less often. Self-reported exposures also varied by race and sex.ConclusionsOur results demonstrate that the distribution of self-reported exposures varied by service era, demographics, deployment, combat experience and military occupation in MVP. Overall, the pattern of findings was consistent with previous population-based studies of US military Veterans.