Polyvinyl alcohol/chitosan (PVA/CS) blend filled with the metal-salt manganese bromide (MnBr2) was prepared using the solution-casting method. The effect of incorporating MnBr2 on the electrical properties of the blend was investigated; with special reference to the effect of dehydration on the dielectric properties. Samples were characterized using XRD, SEM, TGA, and optical studies. Complexation between polymer blend and MnBr2 is confirmed using XRD and optical analysis. A strong absorption band at 5.9 eV (210 nm) and a shoulder-like peak at 4.1 eV (305 nm) were found and explained. In addition, a blue shift is observed for the 305 nm band by the addition of MnBr2 to the blend which confirmed the complexation between MnBr2 and the PVA/CS blend as predicted earlier by XRD data. In addition, MnBr2 doped composites show higher thermal stability than the pure blend. Dielectric constant values are higher than similar (PVA/CS) blend-metal salt composites reported in the literature.