Evolving payment structures have encouraged hospitals to consider the care trajectory of patients requiring post-acute care (PAC), however, investments in transitional care practices have largely been concentrated among exclusive networks of high-volume, “preferred” skilled nursing facility (SNF) partners. Patients with complex social and behavioral health conditions, including those with serious mental illness (SMI), represent a growing proportion of SNF patients. Although care transitions are especially risky for patients with SMI, they may not benefit equally from the improved relational coordination that comes from hospital-SNF preferred provider networks. Using a 100% sample of Medicare claims data, we assessed the role of preferred provider networks on patient choice of SNF using a discrete choice model. Compared to patients without SMI, those with SMI had a significantly lower probability of discharging to their closest preferred SNF. However, this effect was reversed when patients with SMI also had a co-occurring condition targeted by value-based payment programs. Although hospitals will likely continue to invest in relationships that lower their financial risk, the evolving PAC landscape requires more widespread administrative and clinical collaborative efforts that benefit the broader network of consumers by accounting for behavioral and psychosocial needs.