As for the efficient dye-sensitized solar cells (DSSCs), one of the important goals is to increase the light harvesting efficiency to further improve the photoelectric conversion efficiency (PCE). The excellent photoanode materials should possess a uniform porous structure, a large surface area, high crystallinity, and good stability. Herein, the porous TiO2 electrode (named as S-1.5) with the above merits had been prepared by the simple template-assisted method with camphene as the pore-forming reagent. The surface area of the porous TiO2 electrode can be tailored by introducing the amount of camphene. The porous TiO2 layer with the optimal surface area directly adhered on the top of the ultra-thin P25 dense layer had been constructed and this unique electrode with a “double layers structure”, which named as S-1.5/P25. When DSSCs assembled with this photoanode, a desirable PCE of 8.31% had been achieved, which was obviously higher than that of the commercial P25 (7.62%) in parallel. The improved PCE can be attributed to the improved utilization of sunlight, the facilitated photo-generated electron transfer, and the reduced interface resistance. Meanwhile, the related characterization including electrochemical impedance spectroscopy, intensity-modulated photovoltage spectroscopy, and intensity-modulated photocurrent spectroscopy was characterized to explore the possible mechanism.