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Pain catastrophizing is a maladaptive response to pain that amplifies chronic pain intensity and distress. Few studies have examined how pain catastrophizing relates to opioid prescription in outpatients with chronic pain.The authors conducted a retrospective observational study of the relationships between opioid prescription, pain intensity, and pain catastrophizing in 1,794 adults (1,129 women; 63%) presenting for new evaluation at a large tertiary care pain treatment center. Data were sourced primarily from an open-source, learning health system and pain registry and secondarily from manual review of electronic medical records. A binary opioid prescription variable (yes/no) constituted the dependent variable; independent variables were age, sex, pain intensity, pain catastrophizing, depression, and anxiety.Most patients were prescribed at least one opioid medication (57%; n = 1,020). A significant interaction and main effects of pain intensity and pain catastrophizing on opioid prescription were noted (P < 0.04). Additive modeling revealed sex differences in the relationship between pain catastrophizing, pain intensity, and opioid prescription, such that opioid prescription became more common at lower levels of pain catastrophizing for women than for men.Results supported the conclusion that pain catastrophizing and sex moderate the relationship between pain intensity and opioid prescription. Although men and women patients had similar Pain Catastrophizing Scale scores, historically “subthreshold” levels of pain catastrophizing were significantly associated with opioid prescription only for women patients. These findings suggest that pain intensity and catastrophizing contribute to different patterns of opioid prescription for men and women patients, highlighting a potential need for examination and intervention in future studies.