In this letter, a series of A site and B site substituted (1 − x)BiFeO3-(x)BaFe1/2Nb1/2O3 (x = 0.05 to 0.20) (BFO-BFN) ferroelectric materials are designed to serve as photoanode in dye-sensitized solar cells (DSSCs). The formation of mixed structural phase from R3c to R3c + Pm-3m on substitution is confirmed by Rietveld refinement of powder X-ray diffraction data and Raman mode. Tuning the bandgap of BiFeO3 through A and B site substitution is a possible route for improving the power conversion efficiency (PCE). Improvement on the PCE is because of narrowing of bandgap as the function of increase in Fe-O-Fe bond angle and Fe-O bond length along with the decrease in octahedral tilt. The results have shown that the x = 0.20 sample has a maximum of 5.38% PCE. The novel photoanode based on BFO-BFN material could be a specific component of DSSC devices.