Objective: Substance use is the leading cause of preventable deaths in the U.S. Chronic pain is associated with risky substance use. Black individuals experience substantial disparities in pain and substance use outcomes and treatment. Maladaptive psychological reactions to chronic pain, such as pain catastrophizing and pain anxiety, can increase substance use among White individuals. However, no research to date has tested this among Black individuals. This study is the first to test the relationships between pain catastrophizing, pain anxiety, and substance use among Black individuals with chronic pain who use opioid medications. Method: Black adults with chronic pain who use opioids (N = 401) completed online measures of pain catastrophizing (Brief Pain Catastrophizing Scale); pain anxiety (Pain Anxiety Symptom Scale Short Form-20); risky use of alcohol, tobacco, e-cigarettes, cannabis and opioids (Alcohol, Smoking and Substance Involvement Screening Test); and opioid dependence (Severity of Dependence Scale). We conducted zero-inflated and hierarchical regressions to test associations between pain catastrophizing, pain anxiety and substance use (risky use; general use vs. nonuse) above that of demographics, pain intensity and pain interference. Results: Pain catastrophizing was uniquely associated with risky use of all substances (βs = .03–.09, ps < .001–.02), opioid dependence (β = .13, SE = .05, p = .01), and use (vs. nonuse) of tobacco, alcohol and opioids (βs = .07–.11, ps < .001–.02). Pain anxiety was uniquely associated with tobacco use (vs. nonuse; β = −.02, SE = .01, p = .04) and severity of opioid dependence (β = .21, SE = .01, p < .001). Conclusion: Pain catastrophizing and, to a lesser degree, pain anxiety may be useful intervention targets for this underserved and understudied population. Addressing them may help reduce additional health complications and costs associated with substance use-related risk and dependence.