A facile inside-out Ostwald ripening route to the morphology-controlled preparation of TiO₂ microspheres is developed. Here, TiO₂ hollow microspheres (HM) and solid microspheres (SM) are prepared by adjusting the volume ratio of isopropanol (IPA) to acetylacetone (Acac) in the solvothermal process. During the formation process of HM, precipitation of solid cores, subsequent deposition of outer shells on the surface of cores, and simultaneous core dissolution and shell recrystallization are observed, which validate the inside-out Ostwald ripening mechanism. Design and optimization of the properties (pore size, surface area, and trap state) of TiO₂ microspheres are vital to the high performance of dyesensitized solar cells (DSSCs). The optimized TiO₂ microspheres (rHM and rSM) obtained by post-processing on recrystallization, possess large pore sizes, high surface areas and reduced trap states (Ti³⁺ and oxygen vacancy), and are thus ideal materials for photovoltaic devices. The power conversion efficiency of DSSCs fabricated using rHM photoanode is 11.22%, which is significantly improved compared with the 10.54% efficiency of the rSM-based DSSC. Our work provides a strategy for synthesizing TiO₂ microspheres that simultaneously accommodate different physical properties, in terms of surface area, crystallinity, morphology, and mesoporosity.