Novel proton conducting solid polymer electrolytes based on Poly Vinyl Alcohol (PVA) with Malonic acid and PVA with Succinic Acid as a dopant are prepared by solution cast technique with varying doping concentrations up to 40 at.%. The electrical conductivity and optical absorption of pure PVA and doped PVA electrolytes are investigated. DC conductivity behavior is studied in the range 303K to 373K. It is found that PVA: Malonic acid (70:30) & PVA: Succinic acid (70:30) electrolytes exhibited the maximum conductivity. The electrical conductivity initially increased with increasing dopant concentration and then showed a decrease beyond 30 at.% concentration. The increase in conductivity is attributed to the formation of charge transfer complexes while the decrease in concentrations above 30 at.% is due to segregation. Optical absorption studies are made in the wavelength range 200-600nm and the values of optical band gap (direct and indirect) are estimated. The results obtained are presented and discussed.