Synthesis and dielectric studies on a new PEO-PVP blended Na + ion conducting solid polymer electrolytes (SPEs): (1- x )[75PEO:25NaPO 3 ]+ x PVP, where x in wet. %, are reported. PEO-PVP blended Na + ion conducting SPEs are synthesized using recently developed hot-press method in place of traditional solution cast technique. Structural characterization has been carried out using XRD technique. The some basic ion transport parameters viz. ionic conductivity (σ), activation energy ( E a ) and dielectric constant (e*) have been characterized using different experimental techniques.