γ‐Aminobutyric acid (GABA) is a functional amino acid that is widely present in Chinese rice wine. In this study, high‐performance liquid chromatography coupled with ultraviolet detection (HPLC‐UV) was established for the determination of γ‐aminobutyric acid in 22 Chinese rice wines collected from the Shaoxing region of China. Furthermore, the evolution of GABA was studied in Chinese rice wine during primary and post‐fermentation process. Results showed that the HPLC method was reliable with good linearity, accuracy, precision and stability. Additionally, the GABA content varied significantly in the 22 Chinese rice wines, and the content was much higher in wine samples with long aging periods. Regarding the evolution of GABA in Chinese rice wine during the brewing process, the level slowly increased during primary fermentation. A decrease in GABA was observed in the wine at the early stage of the post‐fermentation process. However, a marked increase on the GABA content occurred in wine at the late stage of post‐fermentation. The findings from this study are that HPLC can be successfully applied to determine GABA in Shaoxing brewed rice wines, and further provide useful information on quality control of such wines. Copyright © 2017 The Institute of Brewing & Distilling