A nanostructured, tri-layer TiO2 photoanode consisting of a rice grain-shaped (RG), electrospun TiO2 nanofiber layer (NF) sandwiched between two TiO2 nanoparticle (NP) layers has been successfully used for the efficiency enhancement in quasi-solid-state electrolyte-based dye-sensitized solar cells (DSSCs). A polyethylene oxide-based quasi-solid-state or gel electrolyte with binary iodide salts with optimized composition was employed as the electrolyte. The solar cell parameters of this DSSC were compared with DSSCs fabricated using conventional NP TiO2 photoanode. While the DSSCs fabricated with conventional NP photoanode showed an average efficiency of 5.76% with J (sc) of 12.12 mA cm(-2) and V (oc) of 718.7 mV, the DSSCs fabricated with three-layer composite TiO2 nanostructured photoanode (TiO2 NP/RG/NP) showed an enhanced efficiency of 6.90% with J (sc) of 16.93 mA cm(-2) and V (oc) of 672.3 mV. This shows that the three-layered composite photoanode with "rice grain-shaped" nanostructure is much superior to single-layered TiO2 nanoparticle photoanode prepared by conventional method and evidently contributes to the efficiency enhancement by enhanced light harvesting by scattering. Post-treatment of the three-layer photoanode with TiCl4 further enhanced the efficiency up to an impressive 7.30% which is among the highest for a quasi-solid-state DSSC.