The main purpose of this study was to test the relationship between past-year suicide attempt (SA) and past-year opioid misuse among Veterans at high risk of suicide who reported using at least one illicit substance or alcohol in the past year. Baseline data from 130 high suicide-risk Veterans (n = 39 past-year opioid misusers; n = 91 past-year users of other substances) who enrolled in a randomized controlled trial testing adjunctive Mindfulness-Based Cognitive Therapy to Prevent Suicidal Behavior were used. Information was collected on a semi-structured interview that included the Columbia-Suicide Severity Rating Scale to collect suicide attempt history. Past-year opioid misusers, compared to those who used at least one other illicit substance or alcohol in the past year, were more likely to have made a past-year SA. Past-year opioid misuse remained associated with past-year SA in multivariate analysis that included other known risk factors for SA. Our findings show a robust link between near-term SA and opioid misuse in Veterans.