A new donor-acceptor polymer poly (3-Cyanopyridine-fluorene) (PCP) was designed, and synthesized by using Suzuki coupling reaction. The synthesized polymer, PCP hybridized TiO2 nanocomposites were prepared from the blends of TiO2/PCP by varying the PCP percentage (0.3-0.6 wt%). Presence of polymer (PCP) in small quantity does not affect the morphology of the electron transport layer (ETL) and XRD spectra showed the retention of crystalline characteristics of the ETL after modification. Moreover, the fabricated DSSCs made of these ETL with N719 sensitizer reveals a greater dye adsorption ability caused due to the profound improvement in basicity of TiO2 after modification. Among the various PCP (wt%) doped ETL, DSSC fabricated for 0.5 wt% PCP doped ETL showed an optimized device efficiency up to 6.4% which is about 45% more efficient than unmodified ETL. It is evident that the modification of ETL with PCP not only helps for the better dye adsorption but also assist for the improved electron lifetime which resulted in the enhanced efficiency of the device.