In United States military veterans, chronic pain represents a risk factor for opioid and alcohol misuse, yet few studies have examined interactions among chronic pain, opioid prescription, and opioid and alcohol misuse. Previous work found substantial risk of co-morbid alcohol and opioid misuse in a community sample of opioid-prescribed individuals with chronic pain, a finding expanded upon here. Specifically, 211 veterans assessed within a chronic pain treatment service for opioid-prescribed individuals completed self-report measures of opioid misuse, alcohol misuse, pain intensity, depression, pain catastrophizing, and post-traumatic stress symptoms (PTS). Based on the substance misuse measures, 32% (n = 68) were misusing neither opioids nor alcohol, 23% (n = 48) were misusing both opioids and alcohol, 40% (n = 84) were misusing opioids alone, and 5% (n = 11) were misusing alcohol alone. Group comparisons indicated that individuals not misusing either substance were less distressed in comparison to those who were misusing opioids alone or both substances. The latter groups differed in PTS. Overall, misuse frequencies mirrored previous work, with approximately 1 of 3 misusing opioids and approximately 1 of 5 misusing both substances. There is a need for increased focus on both polysubstance misuse and the development of integrated treatment.