Deoxynivalenol (DON) is one of the most commonly found mycotoxins across the world, and it mainly contaminates staple food crops. This study aims to evaluate the dietary exposure of DON and to provide a geographical profile of DON exposure in China. The concentrations of DON and its acetylated derivatives in 15,004 cereal samples (10,192 wheat flour, 1750 maize meal, 892 oat flakes, and 2170 polished rice) were collected from 30 provinces, autonomous regions, or municipalities across China during 2010–2017, through a national food safety risk surveillance system. The consumption data for cereals were obtained from China National Nutrition and Health Survey in 2002, and 67,923 respondents from the same 30 regions were included in the analysis. Among all the cereals considered, the concentration was the highest in wheat flour, with the mean concentration of 250.8 μg/kg. Applying a worst-case scenario, some individuals were possibly at risk, but the probability of acute effects was low. The mean and median exposure for the entire population was 0.61 and 0.36 μg/kg bw/day, respectively, below the (PM) TDI, indicating an acceptable overall health risk in Chinese population. Wheat contributed to 86% of the total DON exposure. Significant discrepancy was observed between the exposure and the contamination of DON. The high-exposure cluster area was in northern China, whilst the most seriously contaminated regions were all located in the southeast, which formed a seriously contaminated area.