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Positive social relationships are linked to better health outcomes. Beyond global evaluations of relationship quality, little is known about how specific interpersonal processes may influence biological pathways promoting optimal health outcomes. Perceived partner responsiveness (PPR) is an interpersonal process through which an individual comes to believe that their romantic partner attends to and supports core aspects of their self, leading them to feel understood, validated, and cared for by their partner. The goals of this study were to assess whether PPR would be associated with changes in circulating inflammatory biomarkers over time, and whether this association would be more pronounced in the context of chronic caregiving stress among middle-aged mothers. Participants were 169 partnered mothers caregiving for an adolescent or young adult with a neurodevelopmental disorder, the higher caregiving stress group, or a typically developing adolescent or young adult, the lower caregiving stress group. In this 30-month longitudinal study, participants completed a daily diary assessment of PPR and negative spousal interactions and provided blood samples for inflammatory biomarkers analysis. Results indicated that higher PPR was associated with smaller increases in inflammation over time, over and above differences in negative spousal interactions. Although caregiving stress was associated with higher inflammation at baseline, it was not associated with change in inflammation over time. Furthermore, caregiving stress did not moderate the association between PPR and inflammation. These findings suggest that perceived partner responsiveness is a positive interpersonal process that may play a unique role in the health effects of close relationships.