Background and aims: Despite increases in opioid prescribing and related morbidity and mortality, few studies have comprehensively documented harms across opioid types. We examined a population‐wide indicator of extramedical pharmaceutical opioid‐related harm to determine if the supply‐adjusted rates of ambulance presentations, the severity of presentations or other attendance characteristics differed by opioid type. Design: Retrospective observational study of coded ambulance patient care records related to extramedical pharmaceutical opioid use, January 2013 to September 2018. Setting: Australia Cases: Primary analyses used Victorian data (n = 9823), with available data from other Australian jurisdictions (n = 4338) used to determine generalizability. Measurements: We calculated supply‐adjusted rates of attendances using Poisson regression, and used multinomial logistic regression to compare demographic, presentation severity, mental health, substance use and other characteristics of attendances associated with seven pharmaceutical opioids. Findings: In Victoria, the highest rates of attendance [per 100 000 oral morphine equivalent mg (OME)] were for codeine (0.273/100 000) and oxycodone (0.113/100 000). The lowest rates were for fentanyl (0.019/100 000) and tapentadol (0.005/100 000). Oxycodone–naloxone rates (0.031/100 000) were lower than for oxycodone as a single ingredient (0.113/100 000). Fentanyl‐related attendances were associated with the most severe characteristics, most likely to be an accidental overdose, most likely to have naloxone administered and least likely to be transferred to hospital. In contrast, codeine‐related attendances were more likely to involve suicidal thoughts/behaviours, younger females and be transported to hospital. Supply‐adjusted attendance rates for individual opioids were stable over time. Victorian states were broadly consistent with non‐Victorian states. Conclusions: In Australia, rates and characteristics of opioid‐related harm vary by opioid type. Supply‐adjusted ambulance attendance rates appear to be both stable over time and unaffected by large changes in supply.