The present study deals with the multiple heavy metal pollution in Enshi, which is known as "the capital of Se in China". We observed elevated concentrations of heavy metals (Mo, Cd) in shales, soils and rice plants collected from Enshi. We demonstrated that the weathering of Se-rich rocks could release substantial amount of heavy metals to the soils in Enshi. Except Cd and Mo, the other heavy metals have low bioavailability. The bioavailiable fractions of Cd and Mo account for 41.84%, 10.75% of total Cd and Mo in soils, respectively. Correspondingly, high mean BAFs of Cd (0.85) and Mo (0.71) were found in rice. Other heavy metals showed low BAFs in rice. The extremely enrichment of Se in soils could inhibit the uptake of Cu and Hg. The mean PDI of Se, Cd, Mo, Zn, Cu are 252 ± 184, 314 ± 301, 1774 ± 1326, 7.4 ± 1.68, 0.87 ± 0.35 mg/day. High risk of Cd and Mo through consumption of local rice were found for Enshi residents. This study firstly demonstrated that heavy metal pollution can be serious in Se-rich areas.