Making new acquaintances requires learning to recognise previously unfamiliar faces. In the current study, we investigated this process by staging real-world social interactions between actors and the participants. Participants completed a face-matching behavioural task in which they matched photographs of the actors (whom they had yet to meet), or faces similar to the actors (henceforth called foils). Participants were then scanned using functional magnetic resonance imaging (fMRI) while viewing photographs of actors and foils. Immediately after exiting the scanner, participants met the actors for the first time and interacted with them for 10 min. On subsequent days, participants completed a second behavioural experiment and then a second fMRI scan. Prior to each session, actors again interacted with the participants for 10 min. Behavioural results showed that social interactions improved performance accuracy when matching actor photographs, but not foil photographs. The fMRI analysis revealed a difference in the neural response to actor photographs and foil photographs across all regions of interest (ROIs) only after social interactions had occurred. Our results demonstrate that short social interactions were sufficient to learn and discriminate previously unfamiliar individuals. Moreover, these learning effects were present in brain areas involved in face processing and memory.