The structures of molten and crystalline states of Rb2ZnCl4 have been simulated by molecular dynamics with the effective potentials which had been applied in the simulations of RbCl and ZnCl2 systems.Six radial distribution functions (RDF) simulated are presented,of which Zn-Cl and Rb-Cl RDFs are in good accordance with the recent EXAFS experimental results.Based on the instantaneous configurations given by the simulations,the local structures in molten and crystalline states have been studied with bond-order parameter method.The results show that the Zn atom and its neighboring Cl atoms form a stable tetrahedral structure,and the Zn/Cl tetrahedral structures in molten Rb2ZnCl4 are stabler than those in molten ZnCl2.The presence of a good quantity of stable (ZnCl4)2- units without apparent network-like structures is the typical characteristics of the molten Rb2ZnCl4.The simulations for crystalline state did not describe the complex coordinations between Rb and Cl atoms in detail,which showed that the two-body effective potentials are not enough to simulate the behaviors of Rb atoms in the crystalline Rb2ZnCl4.