The White-faced Whistling Duck is a waterfowl species lacking any differences in ornamentation, coloration, size or behavior between the sexes. For distant communication, this species uses loud whistles. We analyzed 12 spectral parameters of 344 whistles from 23 captive adult ducks (14 males and 9 females). Discriminant analysis showed 94% correct assignment to an individual (N = 279 calls from 14 birds; 15–22 calls per bird). Separately for 8 males (162 calls) and for 6 females (117 calls), discriminant analysis showed 99% and 93% correct assignment to individuals respectively. Discriminant analysis for sex (N = 86; 3 calls from each of 14 males and 5 calls from each of 9 females) showed 100% correct assignment. Intersexual differences were governed by frequency parameters, the values of which were significantly higher in females than in males. Cluster analysis showed that differences between sexes were expressed significantly more strongly than the individual differences. The fact that the “acoustical keys” differed as regards the identification of individual birds or their sex may significantly enhance the reliability of acoustical recognition systems in the White-faced Whistling Duck. The data are discussed in the context of the biology of the White-faced Whistling Duck and significant intersexual differences in syringial and tracheal anatomy, which may be responsible for the sharp distinctions between the sexes in the calls of this species.