Structural, thermal, and electrical properties of solid composite polymer electrolytes based on poly (vinyl alcohol) complexed with sodium salicylate were studied. The polymer electrolytes at different weight percent ratios were prepared by solution casting technique. The changes in the structures of the electrolytes were characterized by XRD, which revealed the amorphous domains of the polymer which increased with increase of sodium salicylate concentration. The complexion of the polymer electrolytes were confirmed by FTIR studies. Thermal gravimetric analysis (TGA) was used to study the thermal stability of the polymer below 523 K. The decomposition decreases with increasing sodium salicylate concentration. The conductivity and dielectric properties were measured using an impedance analyzer in frequency range of 20 Hz to 1 MHz and narrow temperature range of 303 to 343 K. The conductivity increased with increase of sodium salicylate concentration and temperature. The dielectric constant and dielectric loss increased with the increase in temperature and decreased with the increase in sodium salicylate concentration.