Perchlorate is an environmental contaminant that has both natural and anthropogenic sources. Widespread contamination of various foods with perchlorate can be caused by water, soil, and fertilizer. Because of concerns about the health effects of perchlorate, attention has focused on its occurrence in food and potential human exposure. In this study, the dietary exposures of Chinese adult males and breastfed infants to perchlorate were evaluated using data from the sixth China Total Diet Study and the third National Breast Milk Monitoring Program conducted between 2016 and 2019. In the sixth China Total Diet Study, perchlorate was detected in 94.8 % of composite dietary samples (n = 288) from 24 provinces in China, while for the third National Breast Milk Monitoring, perchlorate was found in 100 % of pooled breast milk samples (n = 100) collected from 100 cities/counties in China. Vegetables were found to be the main source of dietary exposure for Chinese adult males. Furthermore, the concentrations in breast milk between urban (n = 34, mean: 38.6 μg/L) and rural (n = 66, mean: 59.0 μg/L) regions from 100 cities/counties in China were not significantly different. On average, the estimated daily intake of Chinese adult males (18–45 years) to perchlorate was 0.449 μg/kg bw/day, while that for breastfed infants (0–24 months) was 3.21–5.43 μg/kg bw/day. The exposure to perchlorate in breastfed infants was almost 10-fold greater than that of Chinese adult males.