Prescription opioid analgesic misuse and addiction are a significant public health concern in the USA. Through their concurrent roles as prescribers and public health stewards, medical toxicologists (MTs) have a unique perspective on this issue. They represent a physician group with a particular interest in prescription drug monitoring programs (PDMPs) because of their subspecialty knowledge of the negative consequences of opioid overprescribing in terms of misuse, diversion, addiction, and overdose death. This study surveyed a national sample of MTs about their opioid prescribing patterns and their knowledge and use of PDMPs. A link to a Web-based survey was disseminated by email to the physician membership of the American College of Medical Toxicology. The survey assessed the circumstances and details of the respondents prescribing practices for opioids and their knowledge and use of PDMPs. This included focused questions regarding their perceived limitation of their current PDMP. Responses were received from 205/445 surveys (46 %), representing responses from 35 states. The majority (78 %) of MTs responding to the survey reported that they primarily practice emergency medicine. Although awareness of PDMPs, in general, was high, approximately 25 % reported no knowledge of or did not have access to their state's PDMP. Barriers to use included time and complexity required to access relevant information. MTs prescribe opioids primarily to patients in the Emergency Department (ED) for acute pain or acute exacerbations of chronic pain. MTs are generally aware of PDMPs, although many were unaware of or not using their state-based PDMPs when prescribing opioids in clinical practice.