OBJECTIVE: To isolate and purify three principal degraded impurities of mitiglinide calcium (impurity A, B, C) and identify their structures, establish HPLC method for content determination of impurity A,B,C. METHODS: Mitiglinide calcium was used as raw material and reacted with acid; 3 impurities were then separated by HPLC and their structures were elucidated by IR, MS, 1H NMR, 13C NMR, LC-ESI-MS and ORD. 3 impurities of 3 batches of mitiglinide calcium were determined, and the determination was performed on Agilent Extend-C18 column with mobile phase consisted of 0.01 mol/L sodium acetate solution-acetonitrile-triethylamine (60 ∶ 40 ∶ 0.1, pH=3.0) at the flow rate of 1.0 ml/min. The detection wavelength was set at 210 nm and sample size was 20 μl. The response tests of 3 impurities and mitiglinide calcium were conducted. RESULTS: After treated with acid, impurity A, B, C had been obtained, and their purity were 99.05%, 98.87%, 99.98%, respectively after isolation and purification; after identifying the structure, 3 impurities were S-2-bezylsuccinic acid, S-2-bezylsuccinic acid-4-methyl ester, methyl (2S)-2-benzyl-3-(cis-hexahydroisoindolin-2-ylcarbonyl) propionate; methodological study of content determination of impurities were all up to the requirement. The linear range of impurity A, B, C were 0.387 5-3.875, 0.395-3.95 and 0.392 5-3.925 μg/ml (all r were 1.000 0). The response value of impurity A, B, C and mitiglinide calcium were 2.316 1, 2.636 1, 2.617 8 and 2.620 4, respectively. CONCLUSIONS: The structures of 3 principal degraded impurities of mitiglinide calcium have been identified and confirmed; the content of them can be determined by HPLC main component self-comparison method.