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A trilaminar layer photoanode for dye-sensitized solar cells (DSSCs) was constructed using urchin-like TiO2 hierarchical microspheres and P25. The top layer made of hierarchical microspheres enhanced light scattering; the middle layer consisting of P25 and as-prepared microspheres is a multifunctional layer for DSSCs, high adsorption ability to the dye, light scattering ability, and slow recombination rates coexistence; the bottom layer used P25. The DSSCs based on the photoanode with tripartite-layers structure exhibited a much higher short-circuit photocurrent density of 18.97 mA cm–2 and energy conversion efficiency of 8.80%, which indicated a 36% increase in the conversion efficiency compared to those of the P25 electrode (14.51 mA cm–2, 6.50%). The great improvements of photocurrent density and energy conversion efficiency for hierarchical TiO2 microspheres were mainly attributed to a considerable surface area, a higher light scattering ability, and slower electron recombination rates for the former.