Background and Objectives Prescription Drug Monitoring Programs (PDMP) detect high‐risk prescribing and patient behaviors. This study describes the characteristics associated with documented PDMP access when prescribing opioids. Methods Retrospective chart review of 695 opioid prescriptions written from inpatient and outpatient medical and psychiatric settings. Data were abstracted and analyzed to identify characteristics associated with documented PDMP access. Results One‐third of the charts had PDMP access documented within the week of opioid prescription; 12% showed PDMP consultation on the same day. Services varied greatly from 10.5% (inpatient medicine) to 57% (inpatient psychiatry) with regard to same‐day PDMP access (P < .0001). Patient characteristics associated with PDMP access include having acute pain, current mental health treatment, and current and past substance use disorders (all P < .05). Logistic regression modeling identified three variables associated with the odds of PDMP access (c‐statistic = 0.66): if the prescription originated from the inpatient medicine unit (odds ratio [OR] = 0.47, 95% confidence interval [CI] = 0.32, 0.68), or if the patient received a prescription for an opioid in the past 30 days (OR = 0.30, 95% CI = 0.10, 0.90) or had a urine toxicology screen in the past year (OR = 2.00, 95% CI = 1.40, 2.90). Discussion and Conclusions Utilization of the PDMP varied by specialty and setting. Scientific Significance This study is among the first to compare rates of PDMP access in a large sample by specialty and practice setting in a healthcare system with a policy requiring its access and appropriate documentation. With less than one‐third adherence to the policy, additional steps to increase consistent PDMP access are warranted. (Am J Addict 2021;00:00–00)