One important issue in future scenarios predominantly using renewable energy sources is the electrochemical storage of electricity in batteries. Among all rechargeable battery technologies, Li-ion cells have the largest energy density and output voltage today, but they have yet to be optimized in terms of capacity, safety and cost for use as stationary systems. Recently, sodium batteries have been attracting attention again because of the abundant availability of Na. However, much work is still required in the field of sodium batteries in order to mature this technology. Sodium superionic conductor (NASICON) materials are a thoroughly studied class of solid electrolytes. In this study, their crystal structure, compositional diversity and ionic conductivity are surveyed and analysed in order to correlate the lattice parameters and specific crystal structure data with sodium conductivity and activation energy using as much data sets as possible. Approximately 110 compositions with the general formula Na 1 + 2 w + x − y + z M w ( II ) M x ( III ) M y ( V ) M 2 − w − x − y ( IV ) ( SiO 4 ) z ( PO 4 ) 3 − z were included in the data collection to determine an optimal size for the M cations. In addition, the impact of the amount of Na per formula unit on the conductivity and the substitution of P with Si are discussed. An extensive study of the size of the structural bottleneck for sodium conduction (formed by triangles of oxygen ions) was carried out to validate the influence of this geometrical parameter on sodium conductivity.