The present MD simulations are motivated by the recent experimental studies by Nalbandyan et al. , who synthesized a fast Na + -conducting solid (0.04 S/cm at 573 K comparable with the β-alumina ) of the formula Na 2 LiFeTeO 6 . The material is isostructural with heterovalence analogs of A 2 M 2 TeO 6 (A = Na, K ; M = Ni, Zn, Co, and Mg), consisting of edge-sharing LiO 6 , FeO 6 and TeO 6 octahedral brucite-like layers spanning the ab-plane, in which Te alternates with Li or Fe. The brucite-like octahedral layers are not identical along the c-axis, unlike the structure A 2 Ni 2 TeO 6 (A = Na, K), where the Na + ions occupy the inter-layer. The present study provides full inter-atomic potentials and fresh insights on ion transport.