What determines if the first interaction between strangers will be a pleasant experience? An experiment was conducted to investigate the extent to which the perceived quality of an interaction is influenced by conversation content and context, and this paper documents the physiological changes that are likely to play a role in establishing rapport. Females who did not know each other met in pairs and conducted a gossip- or creativity task, either face-to-face or online. The conversation content had no effect on the quality of online interactions. However in the face-to-face condition gossip was associated with better interaction quality. Tonic electrodermal activity steadily declined throughout the interaction, while phasic electrodermal activity first peaked and then returned to baseline. Neither were related to perceived interaction quality. Heart rate variability (HRV) dropped at first but then remained stable. A smaller drop in HRV drop corresponded to higher ratings of rapport and liking. Together these results suggest that gossip can improve the quality of a face-to-face interaction between strangers, and support the conjecture that parasympathetic activity is a marker of human openness to social engagement.