Deoxynivalenol (DON) together with its acetylated derivatives cause detrimental effects on human health, and the purpose of this study was to assess the prevalence of DON and its acetylated derivatives from grains and grain products in Zhejiang province, China, and to assess the risk of DON and its acetylated derivatives due to multiple consumptions of grains and grain products among the Zhejiang population. Food samples numbering 713 were collected, and the LC-MS/MS method was used to determine the toxins. The levels of toxins from grains and grain products were relatively low: DON was the toxin at the highest levels. The food frequency questionnaire was used to collect food consumption data. The result of exposure assessments showed that the population was overall at low levels of toxin exposure. The probable mean group daily intake of toxins was 0.21 μg/kg bw/day, which was far from the group provisional maximum tolerable daily intake of 1 μg/kg bw/day, but 0.71% of participants were at high exposure levels. Rice and dried noodles (wheat-based food) were the main sources of toxin exposure, and reducing the consumption of rice and dried noodles while consuming more of other foods with lower levels of toxins is recommended.