A total of 969 corn kernels and corn-based products collected from 24 provinces in China between 2008 and 2011 were analyzed for deoxynivalenol, deoxynivalenol 3-glucoside, 3-acetyl-deoxynivalenol, and 15-acetyl-deoxynivalenol by ultraperformance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS). Deoxynivalenol was the predominant mycotoxin detected. A total of 29 out of 969 samples (corn kernels: 9/289, mean = 1884 μg/kg; corn-based products: 20/680, mean = 1580 μg/kg) contain deoxynivalenol at the levels exceeding the Chinese regulatory limit of 1000 μg/kg for deoxynivalenol in corn. The average relative concentration ratios (%) for deoxynivalenol 3-glucoside/deoxynivalenol for all four years were 25% ± 5% in corn kernels and 34% ± 4% in corn-based products. The results of this study indicate that it is necessary to include deoxynivalenol 3-glucoside in both risk assessment of deoxynivalenol and its derivatives and development of the tolerance limit for deoxynivalenol in Chinese corn kernels and corn-based products.