A general synthesis of inorganic single-crystalline hollow spheres has been achieved through a mechanism analogous to the Kirkendall effect, based on a simple one-step laser process performed at room temperature. Taking TiO2 as an example, we describe the laser process by investigating the influence of experimental parameters, for example, laser wavelength, laser fluence/irradiation time, liquid medium, and concentration of starting materials, on the formation of hollow spheres. It was found that the size-tailored TiO2 hollow spheres demonstrate tunable light scattering over a wide visible-light range. Inspired by the effect of light scattering, we introduced the TiO2 hollow sphere's scattering layer in quantum dot-sensitized solar cells and achieved a current notable 10% improvement of solar-to-electric conversion efficiency, indicating that TiO2 hollow spheres are potential candidates in optical and optoelectronic devices.