This study aims to examine the effect of the non-Saccharomyces yeast Saccharomycopsis fibuligera on the sensory quality and flavour characteristics of a sweet rice alcoholic beverage. The strain S. fibuligera was isolated from a traditional Chinese hand-made starter with the purpose to improving sweet rice wine fragrance. Here, sweet rice wines were produced by six combinations of three species of fermentation strains, including S. fibuligera, Rhizopus and Saccharomyces cerevisiae, for evaluation. The study results showed significant diversities within these rice wines based on indicators including the score of quantitative descriptive analysis and volatile variety and content as well as odour activity value (OAV). Quantitative results showed that 43 volatile compounds were identified by headspace-solid phase microextraction with gas chromatography-mass spectrometry among samples. Based on the principal component analysis and OAV calculation, the two samples (S-2 and S-3) fermented with S. fibuligera and Rhizopus possessed high scores and were distinguished from the others, and ethyl butanoate, ethyl hexanoate, β-phenylethyl alcohol and 1-octen-3-one with high OAVs were responsible for the key aroma of sweet rice wine fermented with S. fibuligera. Co-inoculating S. fibuligera, Rhizopus or/and S. cerevisiae generated more pleasant aroma compounds in a sweet rice alcoholic beverage than when inoculated individually.