This paper describes the first implementation of the aliphatic polycarbonate PTMC – that has previously been successfully applied to lithium polymer batteries – as a non-polyether host matrix in solid-state sodium batteries. Despite higher glass transition temperatures of PTMC–NaTFSI and PTMC–NaClO4 electrolytes than their Li-containing counterparts, the ionic conductivities were found to be similar to the equivalent Li salt electrolytes. Finally, the functionality of PTMC–NaTFSI was demonstrated through cycling of Na/Prussian blue half-cells displaying high discharge capacities and limited polarization at C/10 and 60°C.