The title compound, (Na1/3Li2/3)(Li2,Cr)(MoO4)3, was prepared by solid-state reaction and characterized by X-ray diffraction. The compound crystallizes in the orthorhombic space group Pnma with a = 5.100(2) A, b = 10.483(2) A, c = 17.458(3) A, V = 933.3(4) A3, Z = 2, R(F2) = 3.53%, Rw(F2) = 7.96%, S= 1.042. Its structure is isotypic to Li3Cr(MoO4)3 which has interesting magnetic and conductive proprieties [1,2]. We are interested in this work to its structural investigation and CHARDI and BVS validation. The BVS model is extended to simulate the ionic migration pathways of alkali cations in the anionic framework.