Samhaeju is a traditional Korean noble rice wine, in which its processing is performed at low temperatures for an extended fermentation time and with three brewing steps. In this study, Samhaeju was prepared by different brewing methods that were modified from the method in the literature. Chemical composition of samples were determined to evaluate the quality of the Samhaeju. The Samhaeju was analyzed for pH, total acids, amino nitrogen, Hunter color values, free sugars, organic acids, and volatile components. Before the addition of the second and third mashing, pH values had decreased slightly and total acids had rapidly increased. Free sugar and amino nitrogen contents were high in final product. After addition of the third mashing as the advanced step, a dilution effect was shown. Glucose (A: 0.77-7.0%, B: 0.77-3.81%) was a major free sugar, and lactic acid (A: 0-2,840mg%, B: 0-3,375mg%) was a major organic acid during the entire period of fermentation. Based on principal component analysis of electronic nose data for the components, the stages of Samhaeju fermentation were primarily separated along the first principal component (PC, proportion : 98.67%). The first PC component (PC1) was moved from negative value(-6.16) to positive value(9.00) with increasing fermentation time. The change patterns for pH and total acid during the fermentation period were similar to those of PC1 from the data obtained by electronic nose based on mass spectrometry.