The objective of this study is to investigate tungsten (W) contamination in soil and its enrichment in rice in the area of the world's largest and longest-operating W mines in China. Root zone soil and rice plants were sampled at 15 sites in the agricultural field adjacent to W mines and analyzed for Al, Fe, Mn, Sc, and W contents and W chemical forms in the soil samples and W contents in the rice root, stem, leaf, and grain samples. Results showed that W content in the soil ranged from 3.99 to 43.7 mg kg−1, with more than 90% of W in the residual fraction, showing its low mobility and bioavailability. Average W contents in the rice root, stem, leaf, and grain were 7.06, 2.34, 4.76, 0.17 mg kg−1, respectively. In addition, they were linearly independent of W content and chemical forms in the soil. Average enrichment factor values were 0.39, 0.13, 0.28, and 0.01 for the root, stem, leaf, and grain, respectively. In can be concluded that W mining activity in the Dayu county contaminated the nearby agricultural soil and led to W bioaccumulation in the rice. This may pose a health risk to residents via food and soil ingestion, which should be a focus of scrutiny.