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Background and aims: Extended‐release naltrexone (XR‐NTX) and sublingual buprenorphine (SL‐BUP) are both approved for opioid use disorder (OUD) treatment in any medical setting. We aimed to compare the real‐world effectiveness of XR‐NTX and SL‐BUP. Design and setting: This was an observational active comparator, new user cohort study of Medicaid claims records for patients in New Jersey and California, USA, 2016–19. Participants/cases: The participants were adult Medicaid patients aged 18–64 years who initiated XR‐NTX or SL‐BUP for maintenance treatment of OUD and did not use medications for OUD in the 90 days before initiation. Our cohort included 1755 XR‐NTX and 9886 SL‐BUP patients. Measurements: We examined two outcomes up to 180 days after medication initiation: (1) composite of medication discontinuation and death and (2) composite of overdose and death. Findings In adjusted analyses, treatment with XR‐NTX was more likely to result in discontinuation or death by the end of follow‐up than treatment with SL‐BUP: cumulative risk 75.9% [95% confidence interval (CI) = 73.9%, 77.9%] versus 62.2% (95% CI = 61.2%, 63.2%), respectively (risk difference = 13.7 percentage points, 95% CI = 11.4, 16.0). There was minimal difference in the cumulative risk of overdose or death by the end of follow‐up: XR‐NTX 3.9% (95% CI = 3.0%, 4.8%) versus SL‐BUP 3.3% (95% CI = 2.9%, 3.7%); risk difference = 0.5 percentage points, 95% CI = –0.4, 1.5. Results were consistent across sensitivity analyses. Conclusions: Medicaid patients in California and New Jersey, USA, receiving treatment for opioid use disorder stayed in treatment longer on sublingual buprenorphine than on extended‐release naltrexone, but the risk of overdose was similar. Most patients in this study discontinued medication within 6 months, regardless of which medication was initiated. [ABSTRACT FROM AUTHOR]