In this work, carboxymethyl kappa-carrageenan was used as the principle host for developing new biopolymer electrolytes based on the blend of carboxymethyl kappa-carrageenan/carboxymethyl cellulose. The blending of carboxymethyl cellulose into carboxymethyl kappa-carragenan was found to be a promising strategy to improve the material properties such as conductive properties. The electrolyte samples were characterized using Fourier transform infrared spectroscopy, scanning electron microscopy, dynamic mechanical analysis, electrochemical impedance spectroscopy, ionic transference number measurement and linear sweep voltammetry in order to investigate their structural, thermal and electrochemical properties. Impedance study showed that the ionic conductivity increased with the increment of ammonium iodide concentration. The highest room temperature ionic conductivity achieved was 2.41 x 10(-3) S cm(-1) at 30 wt% of the salt. The increment of conductivity was due to the increase of formation of transient cross-linking between the carboxymethyl kappa-carrageenan/carboxymethyl cellulose chains and the doping salt as indicated the T-g trend. The conductivity was also attributed by the increase in the number of charge carriers in the biopolymer electrolytes system. The interactions between polymers and salt were confirmed by FTIR study. The transference number measurements showed that the conductivity was predominantly ionic. Temperature dependent conductivity study showed that conductivity increased with the reciprocal of temperature. The conductivity-temperature plots suggested that the conductivity obeyed the Vogel-Tammann-Fulcher relation and the activation energy for the best conducting sample was 0.010 eV. This system was used for the fabrication of dye sensitized solar cells, FTO/TiO2-dye/CMKC/CMCE-NH4I + I-2/Pt. The fabricated cell showed response under light intensity of 100 mW cm(-2) with efficiency of 0.13% indicating that the blend biopolymer system has potential to be applied in dye sensitized solar cell. (C) 2015 Elsevier Ltd. All rights reserved.