Prescription-related opioid misuse, especially in chronic pain populations, is an ongoing problem and is related to increased mortality. The purpose of this study was to assess the utility of two restructured scales of the MMPI-2-RF: the Personality Psychopathology Five (PSY-5-RF) and the Higher-Order Scales to determine which of their subscales may be beneficial for identifying the risk of opioid misuse in a chronic pain population. A sample of 136 patients with chronic disabling occupational musculoskeletal disorders completed the MMPI-2-RF and the Current Opioid Misuse Measure (COMM) upon admission to a functional restoration program. The PSY-5-RF and H–O subscales were correlated with the baseline COMM scores. Correlation analyses, ROC curve analyses, and multiple binary logistic regression models were developed to determine which subscales were most associated with elevated COMM scores. The results of the regression analyses suggest that Scale elevations on two of the PSY-5-RF Scales and two Higher-Order Scales of the MMPI-2-RF demonstrated significant associations with elevated COMM scores, thus exhibiting the utility of these subscales in identifying the risk of opioid misuse among chronic pain patients. These findings are clinically meaningful in underscoring the importance of identifying specific personality traits as potential predictors of opioid misuse, and identifying those at risk through careful screening. Clinical implications based on each of the PSY-5-RF and H–O scales significantly associated with elevated COMM scores are discussed.