Abstract: Rancidity is a large challenge commonly encountered in Chinese rice wine business. In order to establish a convenient and operable assaying method for detecting main components and rancid constituents of yellow rice wine, HPCE zone electrophoresis was primarily explored involving wavelength, voltage and buffer solution including its kinds, the pH values and the ionic concentration. It was found that ideal electrophoretograms of wine base and its corresponding rancid sample as well as the marketed yellow rice wine could be obtained with wavelength 215nm, 0.075nmol/L of disodic phosphate-sodium tetraborate buffer and 8.0kV of separation voltage. The remarkable differences existed between the rancid sample and the other two. These peaks represented potential rancid constituents of metamorphous Chinese rice wine could be determined by the established HPCE method. The result was helpful for the detection of rancid constituents, the establishment of quality standards and the quality control of Chinese rice wine in the future.