In the present work, a novel pyranose ring laden polymer electrolyte is proposed for all solid Na-ion secondary cells that can operate at moderate temperatures. The prepared fully solid polymer electrolyte film is based on a classic polyethylene oxide (PEO) backbone, homogeneously blended with sodium carboxymethyl cellulose (Na-CMC) and sodium perchlorate. The favourable use of Na-CMC as electrode binder as well as electrolyte additive is evaluated, which would enhance the pathways for forming an optimised electrode/electrolyte interface. The promising prospects of the newly elaborated hybrid electrolyte are investigated by means of galvanostatic charge/discharge cycling in lab-scale cell with TiO2-based or NaFePO4-based working electrodes.