This work developed a novel ternary composite photoanode of dye-sensitized solar cell (DSSC) composed of (i) N-, S-doped titanium dioxide with exposed {001} facet (N-, S-TiO2{001}), (ii) N-, S-doped reduced graphene oxide (N-, S-rGO), and (iii) commercial titanium dioxide (P25). The DSSC device fabricated with the ternary composite photoanode showed the greatest of power conversion efficiency (8.62%) compared to the device fabricated with P25 photoanode (3.20%). This enhancement was attributed to the synergistic effect of the N-, S-TiO2{001} and the N-, S-rGO, which act as an electron enricher and an electron extractor, respectively.