Higher proton conducting polymer blend electrolytes (HPCPBEs) of cornstarch:poly vinyl pyrrolidone (PVP):ammonium thiocyanate (NH4SCN) have been prepared by solution casting technique. Enhancement of amorphous nature of the polymer blend electrolytes have confirmed by X-ray diffraction analysis. The presence of functional groups in Fourier transform infrared spectrum shows the complexation between salt and host polymer matrix. At ambient temperature, 70 wt% NH4SCN mixed composition has obtained the maximum conductivity (1.36 × 10–4 S cm–1). The dielectric properties of the prepared samples have been analysed. The dielectric spectra and modulus spectra reveal the non-Debye behaviour of the polymer electrolytes. Low activation energy (0.14 eV) with regression value of 0.98 has been revealed from temperature dependence of ionic conductivity studies. Wagner’s polarization technique is used to confirm the conductivity due to the ions. Electrochemical behaviour of HPCPBE has been analysed by cyclic voltammetry. An electrochemical cell has fabricated using the HPCPBE and the observed open circuit voltage is 1.15 V.