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Primates were traditionally thought to have a reduced sense of smell. Although there is now evidence that olfaction plays a greater role in primate social life than previously assumed, research on the sense of smell in non-human apes is scarce. Chimpanzees sniff the ground and vegetation on boundary patrols, but the function of this behaviour is unclear. Since chimpanzees are highly territorial and can kill individuals that do not belong to their own community, sniffing might function to gather information about conspecifics, particularly concerning group membership and kinship. To investigate whether chimpanzees recognize group members and kin via olfactory cues, we conducted behavioural bioassays on two groups of chimpanzees at Leipzig Zoo. In a pilot study, we found that chimpanzees responded more strongly to urine than to faeces or body odour. We then presented urine from group members, outgroup individuals and an unscented control in aerated boxes using a simultaneous discrimination task. The first behaviour after a chimpanzee first approached a box was related to olfaction (sniffing, nose within 20 cm, licking) in 83% of cases, highlighting the importance of olfaction as a general investigation mechanism in this species. Chimpanzees sniffed significantly longer at urine stimuli than the control and significantly longer at odours from outgroup individuals than those from group members. Furthermore, the duration of sniffing was positively correlated with relatedness. Our results suggest that chimpanzees use olfactory cues to obtain information about social relationships and fill a gap in our understanding of primate chemical communication.