Interpersonal functioning involves an interplay of subjective perceptions and overt behavior. This study examines alignment between self and informant perceptions of momentary behavior to enrich the nomological networks for the domains of dominance and affiliation. We studied a sample of romantic couples ( N = 210 individuals) who rated their own and their partner’s interpersonal behavior during a 21-day ambulatory assessment (AA) protocol. We used multi-level structural equation modeling to estimate self-informant agreement on averages and variability of dominance and affiliation (between-person level) and on situational shifts in behavior (within-person level). We also examined convergence between self- and informant reported behavior measured by AA with cross-sectional self-report trait dominance, affiliation, and interpersonal problems. Results showed no self-informant agreement on dominance measured by AA, but moderate to strong agreement on affiliation at the between- and within-person levels. Self- and informant reported average affiliation measured by AA correlated with self-reports of trait affiliation, but only AA self-reports correlated with affiliation problems. Both self- and informant report dominance variability, and informant report affiliation variability, correlated with self-report interpersonal distress. Evidence for (mis)alignment in how dominance and affiliation are perceived by self and others have important implications for the role of these behaviors in everyday interpersonal functioning.