The present study reports, for the first time, the strategy of blending three different polymers followed by the doping of an organic nitrogenous compound to develop a solvent-free novel doped multi-polymer blend electrolyte system for dye-sensitized solar cell (DSSC) applications. Precisely, this novel electrolyte consists of poly (ethylene oxide) (PEO) blended with poly (vinylidene fluoride) (PVdF) and poly (capro lactone) (PCL) that is incorporated into the synthesized 2,6-bis (2-thio pyridyl) pyridine (BTPP) along with KI and I-2. The current-voltage (I-V) characteristics of the nanocrystalline DSSC fabricated using the present electrolyte generates a photocurrent of 15.5 mA/cm(2), a photo-voltage of 905 mV, a fill factor of 0.53 and yields an overall energy conversion efficiency of 9.3% under a simulated sunlight radiation of 80 mW/cm(2). The impressive photoelectric performance of the fabricated solar cell is mainly attributed to the synergic effects of the electrolyte composed of the unique blending of three polymers and the electron donicity of BTPP that leads to strongly influence the interaction between the nanocrystalline TiO2 electrode and I-/I-3(-) electrolyte, thereby leading to high conversion efficiency. Published by Elsevier Ltd.