The local structure of molten ZnBr2 was investigated by X-ray absorption fine structure measurements for both Zn and Br above their K-absorption edges at 723 K. The results show that a tetrahedral coordination (ZnBr4)2− exists and most coordinates connect with the next ones through the Br− ion. The two XAFS functions k3χ(k) in the molten ZnBr2 were reproduced by a combination of a molecular dynamics simulation and an ab initio mutiple scattering calculation of X-ray absorption spectrum.