Novel all solid state dye-sensitised photolectrochemical solar cells of the type, FTO–TiO2–dye–PAN, EC, PC, Pr4N+I−, I2–Pt–FTO, have been fabricated and characterised using current–voltage characteristics and action spectra. Liquid electrolyte generally used for such solar cells has successfully replaced by a quasi solid electrolyte comprised of polyacrylonitrile (PAN) with ethylene carbonate (EC) and propylene carbonate (PC) as plasticisers and Pr4N+I−/I2 redox couple with tetrapropylammoniumiodide as the complexing salt. For the polymer electrolyte, the optimum conductivity of 2.95×10−3 S cm−1 was obtained for the electrolyte composition, PAN:EC:PC=15:35:50 (wt.%). The short circuit current density (J SC) and the open circuit voltage (V OC) obtained for an incident light intensity of 600 W m−2 were 3.73 mA cm−2 and 0.69 V, respectively. This corresponds to an overall quantum efficiency of 2.99%. From the action spectrum, the maximum incident photon conversion efficiency (IPCE) of 33% was obtained for incident light of wavelength 480 nm.