While polymer-based solid-state sodium batteries promise both safe operation and utilization of sustainable materials, they are held back by the insufficient ionic conductivity of the involved solid polymer electrolytes (SPEs). In this study, the conductivity and cation transference number are significantly improved through the construction of a composite polymer electrolyte (CPE) system based on poly(trimethylene carbonate) (PTMC) with sodium bis(trifluorosulfonylimide) (NaTFSI), combined with NaAlO2 (NAO) ceramic filler at loadings ranging from 10 to 40 wt%. The NAO-based CPEs show the highest conductivity at 20 wt% NAO, with a Na+ transference number of ∼0.9 at 60 °C also being obtained for the same material, which is notably higher than that for the NAO-free SPE. Solid-state batteries composed of a Prussian white cathode and a Na metal anode and employing these CPEs reach a cycling performance of ∼100–150 mA h g−1 at C/10 and 55 °C for more than 200 cycles without additives or plasticizers, thus opening the door to the potential exploration of CPEs for Na-based battery chemistries.