Deoxynivalenol (DON) is an important mycotoxin produced by Fusarium spp., typically found in cereals, which has garnered considerable research attention. However, the risk assessment of DON exposure to muti-cereal is partial and biased, especially lacking the evaluation of different coarse grains. In this study, we synthesized and compared the presence of the total deoxynivalenol (free, acetylated, and masked) of a total of 372 grain samples (17 different types) based on high-performance liquid chromatography–tandem mass spectrometry (HPLC–MS/MS), as well as assessed the chronic and acute risks of total DON exposure in the Chinese population. DON was found at the highest frequency with an occurrence of 85.8% (319/372), followed by D3G at 17.2% (64/372). In total, 88.7% (330/372) of the grains were co-contaminated with mycotoxins. The DON and D3G contamination correlation coefficient was 0.68 in wheat flour. Moreover, different DON contamination levels were found in black beans (133.5 µg/kg), soybeans (128.7 µg/kg), and black rice (122.1 µg/kg). The DON/D3G/15A/tDON contamination level was significant differently among different coarse grains. Notably, the Monte Carlo model showed that 3.2–5.9% of adolescents consuming wheat flour and noodles suffered a chronic tDON risk.