Pain catastrophization (PC), involving rumination, magnification, and helplessness, can be viewed as a coping strategy associated with chronic pain. PC is considered a driving force in mediating pain-related outcomes, but it is still unclear whether PC mediates the relationship between psychological and sociodemographic factors with chronic pain when considered in a single model. Using baseline data from a parent study, this study examined the effect of positive and negative psychological and sociodemographic factors on pain severity, interference, and jaw limitation mediated by the PC dimensions in a sample of 397 temporomandibular disorder (TMD) participants using structural equation modeling (SEM). SEM revealed that pain severity regressed on age, sex, education, and income; interference regressed on positive and negative psychological factors, education, and income; and jaw limitation regressed on age. The PC dimensions did not individually mediate these relationships. Although they jointly mediated the relationships between negative psychological factors and pain severity and between age and pain interference, the effect size was small, suggesting that PC is not a critical factor in mediating TMD pain outcomes. Reducing negative cognitions, not just PC, may be of greatest benefit to the most vulnerable TMD populations. PERSPECTIVE: This study examines sociodemographic and psychological factors that affect orofacial pain, finding that the pain catastrophizing dimensions do not mediate these relationships. Understanding which factors most strongly affect pain outcomes will help identify targets for intervention to produce the greatest benefit for the most vulnerable persons suffering from pain.