Sodium orthosilicates Na2MSiO4 (M = Mn, Fe, Co and Ni) have attracted much attention due to the possibility of exchanging two electrons per formula unit. They are also found to exhibit great structural stability due to a diamond-like arrangement of tetrahedral groups. In this work, we have systematically studied the possible polymorphism of these compounds by means of density functional theory, optimising the structure of a number of systems with different group symmetries. The ground state is found to be Pc-symmetric for all the considered M = Mn, Fe, Co, Ni, and several similar structures exhibiting different symmetries coexist within a 0.3 eV energy window from this structural minimum. The intercalation/deintercalation potential is calculated for varying transition metal atoms M. Iron sodium orthosilicates, attractive due to the natural abundance of both materials, exhibit a low voltage, which can be enhanced by doping with nickel. The diffusion pathways for Na atoms are discussed, and the relevant barriers are calculated using the nudged elastic band method on top of DFT calculations. Also in this case, nickel impurities would improve the material performances by lowering the barrier heights. Notably, the ionic conductivity is found to be systematically larger with respect to the case of lithium orthosilicates, due to a larger spacing between atomic layers and to the non-directional bonding between Na and the neighbouring atoms. Overall, the great structural stability of the material together with the low barriers for Na diffusion indicates this class of materials as good candidates for modern battery technologies.