The B-site cation ordering in Ba(Zn1/3Nb2/3)O3 was studied using a combination of first-principles energy calculations, a cluster expansion technique, and Monte Carlo simulations. Our calculations indicate that the ground state is a 1:2 ordered hexagonal structure, in contrast to x-ray diffraction observations, but consistent with recent Raman work by Kim et al. The order–disorder transition between the 1:2 ordered phase and the cubic perovskite phase is predicted to occur at approximately 2480 K. This prediction indicates that Ba(Zn1/3Nb2/3)O3 in equilibrium should be fully ordered at all practical temperatures. These results indicate that Ba(Zn1/3Nb2/3)O3, previously considered to be disordered, may be ordered on a local scale, consistent with its good microwave characteristics.