We investigate the ionic conductivity and electronic properties of Na3P using first principle simulations. We found that the atoms were arranged in one layer of Na and P atoms and alternate layers containing Na atoms only. Three possible independent and asymmetric Na diffusion paths exist. In the first two, Na diffusion occurs among sodium atoms in the same layer, while in the third path, Na diffusion occurs among sodium atoms in different layers. Moreover, the activation energies of Na diffusion in the first two paths are much smaller than that of the third. With the introduction of a Na vacancy, a hole state deep in the valence region appears that is responsible for the valence band-edge rising in the center of the Brillouin zone. This sodium vacancy is very likely to play a role in the electron transfer in Na3P. The fast ionic conductivity and considerable electron conductivity make P a promising anode material in the first step of the Na deintercalation process. (C) 2014 Elsevier B.V. All rights reserved.