The literature concerning biological influences on positive social behavior shows that, in nonthreatening contexts, tonic oxytocin (OT) and respiratory sinus arrhythmia (RSA) each predict positive, affiliative behaviors toward certain others and are associated with positive health outcomes. The purpose of this investigation was to determine the degree to which the positive affiliative correlates of OT and RSA can be distinguished when observed at the level of everyday life events. A sample of midlife adults (N = 73) provided tonic indices of these biological characteristics, as well as perceptions of a variety of common life events alongside reports of their emotions during those events. OT and RSA each independently moderated the link between perceived event sociality and positive emotions, whereas only RSA predicted the probability of being with other people during an event. These findings suggest that OT and RSA may each be linked to positive social experiences in complementary yet distinct ways.