Floatstone-like TiO2 microparticles with an efficiently enhanced Mie scattering effect were developed by thermofusing of rutile-type TiO2 submicron particles on the template core of poly(acrylate) microspheres. The light reflectance of the floatstone-like TiO2 microparticles was approximately 10% higher than that of the usual rutile-type TiO2 submicron particles in a wavelength range from 400 to 850nm. The diffuse reflectance of the microparticles is enhanced by the formation of a floatstone-like structure, whereas there is no difference in the specular reflectance of the particles. As an application of the floatstone-like TiO2 microparticles, the contribution of the particles to the light-trapping effect of a solar cell was examined. The power conversion efficiency of the solar cell was enhanced by 22% with the introduction of a light-scattering layer composed of the floatstone-like TiO2 microparticles.