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To clarify the quality characters, understand the genetic diversity and screen elite lines among different oilseed sunflowers, the contents of crude fat, oleic acid, linoleic acid, palmitic acid and stearic acid of 525 oil sunflowers (including 375 germplasm accessions and 150 inbred lines) were detected by near-infrared spectroscopy (NIRS); the genetic variation and correlation analysis of quality traits were also performed. The results showed that oleic acid and linoleic acid had rich diversities with large variation ranges for each material type. Similar to the relation between crude fat content and palmitic acid content, significantly negative relation with high estimated value existed between oleic acid and linoleic acid content, while stearic acid content positively associated with oleic acid and palmitic acid content. Principal component analysis indicated that 5 quality traits were integrated into 2 principal component factors (linoleic acid negative factor and palmitic acid factor) with the contribution rate of 88.191%, which could be used for evaluating sunflower quality. 525 oilseed sunflowers were clustered into 3 groups with obvious differences of quality characters, materials in Group I had high contents of oleic acid and low crude fat, but the opposite was found in Group III. 59 superior quality accessions were obtained using large-scale and rapid near-infrared spectroscopy, and these excellent materials were verified by the traditional national chemical standard method. This research provided materials and significant reference for sunflower genetic research and quality breeding.