Physiological linkage refers to moment-to-moment, time-linked coordination in physiological responses among people in close relationships. Although people in romantic relationships have been shown to evidence linkage in their physiological responses over time, it is still unclear how patterns of covariation relate to in-the-moment, as well as general levels of, relationship functioning. In the present study with data collected between 2014 and 2017, we capture linkage in electrodermal activity (EDA) in a diverse sample of young-adult couples, generally representative and generalizable to the Los Angeles community from which we sampled. We test how naturally occurring, shifting feelings of closeness with and annoyance toward one's partner relate to concurrent changes in levels of physiological linkage over the course of 1 day. Additionally, we examine how linkage relates to overall relationship satisfaction. Results showed that couples evidenced significant covariation in their levels of physiological arousal in daily life. Further, physiological linkage increased during hours that participants felt close to their romantic partners but not during hours that participants felt annoyed with their partners. Finally, those participants with overall higher levels of relationship satisfaction showed lower levels of linkage over the day of data collection. These findings highlight how individuals respond in sync with their romantic partners and how this process ebbs and flows in conjunction with the shifting emotional tone of their relationships. The discussion focuses on how linkage might enhance closeness or, alternatively, contribute to conflict escalation and the potential of linkage processes to promote positive interpersonal relationships. (PsycInfo Database Record (c) 2023 APA, all rights reserved).