To comprehensively and objectively evaluate the quality of different peach varieties, 23 peach varieties from Hunan Province were evaluated for 18 quality indicators. The core evaluation indicators were identified by variability analysis, correlation analysis, and principal component analysis (PCA), and their weights were determined by the entropy weight method. Subsequently, a comprehensive evaluation model of peach quality was established by grey relational analysis (GRA). The results showed significant differences (P < 0.05) in appearance, nutritional quality, and major functional components among the varieties, as well as varying degrees of correlation among the quality indicators. Based on the principal component loading matrix and coefficient of variation analysis, single fruit mass, soluble solids content, glucose content, flavonoid contents, citric acid content, and fruit shape index were identified as core evaluation indicators, with weights of 23.77%, 21.52%, 15.32%, 24.44%, 7.08%, and 7.87%, respectively. Grey relational analysis showed that‘Yanlingjinxiu’ yellow peach, ‘Apple’ peach, and ‘Tianwudi’ peach ranked among the top three in terms of comprehensive quality, while ‘Zhongpan 7’ peach had the worst quality. According to cluster analysis, 23 peach varieties were divided into four categories. Category Ⅰ was rich in total phenolics and anthocyanins, making it suitable for developing high-value-added health products with antioxidant effects. Category Ⅱ had superior comprehensive quality and was suitable for fresh consumption or processing into high-quality not from concentrate (NFC) juice. Category Ⅲ had relatively inferior comprehensive quality and could be considered for processing into products requiring the addition of sugar and acid, such as preserved fruits, jam, fruit wine, and fruit vinegar, thereby maximizing resource utilization. Category Ⅳ had a high solid/acid ratio and excellent flavor, making it suitable for fresh consumption. This study can provide a theoretical basis for the breeding, quality evaluation, and comprehensive utilization of peach varieties in Hunan province.