In this study, porous cationic hydrogen (H+) conducting polymer blend electrolytes with an amorphous structure were prepared using a casting technique. Poly(vinyl alcohol) (PVA), chitosan (CS), and NH4SCN were used as raw materials. The peak broadening and drop in intensity of the X-ray diffraction (XRD) pattern of the electrolyte systems established the growth of the amorphous phase. The porous structure is associated with the amorphous nature, which was visualized through the field-emission scanning electron microscope (FESEM) images. The enhancement of DC ionic conductivity with increasing salt content was observed up to 40 wt.% of the added salt. The dielectric and electric modulus results were helpful in understanding the ionic conductivity behavior. The transfer number measurement (TNM) technique was used to determine the ion (tion) and electron (telec) transference numbers. The high electrochemical stability up to 2.25 V was recorded using the linear sweep voltammetry (LSV) technique.