The Chishui River Basin is one of the core producing areas of high-quality sorghum in China, and strengthening the research on its germplasm resources is of great significance to steadily improve the quality of brewing. This study investigated important agronomic traits such as plant height, ear length, stem diameter, ear type, hull color type, ear grain weight, 1000-grain weight, etc. of 421 local sorghum germplasm resources and starch, tannin, protein, fat and other important components affecting Baijiu quality of 197 germplasm resources were investigated and analyzed. The distribution laws, diversity indices, and phenotypic cluster characteristics of the key traits and Baijiu-making quality were analyzed. The results indicated that genetic diversity indices for key traits and Baijiu-making quality were relatively low overall, while glume color and glume color at flowering stage exhibited higher diversity indices. The genetic diversity index of different quantitative characters ranged from 1.7470 to 2.0432, with an average of 1.9344. The average contents of total starch, amylose, fat, protein and tannin were 65.61%, 9.27%, 4.41%, 9.50% and 1.41%, respectively. Diversity indices for quality traits ranked as follows: amylose content > fat content > protein content > total starch content > tannin content. Grain weight per head contributed the most to the principal component, followed by panicle length and first-order branch length. Cluster analysis of agronomic characters showed that the germplasm could be divided into 3 groups, including 94 in group I, 104 in group II and 223 in group III. The quality characteristics of brewing sorghum were characterized by high total starch content and moderate tannin content.