Progesterone and oestrogen are the main gonadal steroid hormones that regulate the ovarian activity and induce the fertile oestrus period in females. The monitoring of this receptive phase is particularly decisive for captive breeding and is commonly based on the observation of female behavioural patterns that coincide with their hormonal oestrus. However, in the white rhinoceros (WR), a species that is well known for its impaired reproductive rate in captivity, the female behavioural and vocal indicators of receptivity have not been systematically investigated or linked to their hormonal states so far. In order to close this gap, we combined behavioural and acoustic recordings, conducted over an average period of 32 days, with the analysis of faecal progesterone and oestrogen metabolite concentrations (fPM and fEM) in 27 adult Southern white rhinoceros (Ceratotherium simum simum; SWR) females from 10 European zoos. For eight of the study females, we were able to detect a receptive period indicated by their acceptance of sexual behaviour from the bulls. The comparison of behaviour and vocalization between receptive and non-receptive periods in these females demonstrated that particularly presenting and marking behaviour distinctly peaked during the receptive period, indicating the significance of olfactory signalling for female reproductive behaviour. Based on the analysis of fPM profiles, we were able to identify different reproductive states (cycling, non-cycling, pregnant) in 21 of 27 study females. In contrast, fEM profiles proved to be unsuitable for the detection of ovarian activity. For the majority (five of six females for which behavioural receptivity and endocrine cyclicity were determined), a coincidence of their receptive period and the hormonal oestrus, indicated by a nadir in fPM levels, could be detected. Conclusively, this study revealed a comprehensive behavioural repertoire that reflects the hormonal oestrus in SWR females and can therefore be reliably used for non-invasive ex situ reproduction monitoring.