Communication in rhinos is primarily mediated by the vocal and olfactory signals as they have relatively poor eyesight. White rhinos are the most social of all the rhinoceros species, they defecate at common dungheaps and the adult bulls use dung and urine to mark their territory. Chemical communication may therefore be particularly important in the social interactions of white rhinos, and its knowledge could be very helpful in their management and conservation. However, no studies have investigated up until now the olfactory discrimination in any rhinoceros species in the wild. We have experimentally studied the reactions of the wild southern white rhinos (Ceratotherium simum) to the dung of familiar and unfamiliar adult females and adult territorial males. We registered the number of sniffing events, the duration of sniffing and the latency of the vigilance posture from the onset of sniffing. The dung of unfamiliar rhinos was sniffed longer than that of familiar rhinos. The rhinos showed a shorter latency of vigilance posture to the familiar dung of males than that of females. For unfamiliar dung, they displayed a shorter latency of vigilance posture to female than male dung. Our results indicate that the rhinos are able to discriminate the familiarity and sex of conspecifics from the smell of their dung. Olfactory cues could therefore play an important role in the social relationships and spatial organization of the southern white rhinoceros.