The coupling of two semiconducting materials is an efficient method to improve photocatalytic activity via the suppression of recombination of electron-hole pairs. In particular, the coupling between two different phases of TiO2, i.e., anatase and rutile, is particularly attractive for photocatalytic activity improvement of rutile TiO2 because these coupled TiO2 powders can retain the benefits of TiO2, one of the best photocatalysts. In this study, anatase TiO2 nanoparticles are synthesized and coupled on the surface of rutile TiO2 powders using a microemulsion method and heat treatment. Triton X-100, as a surfactant, is used to suppress the aggregation of anatase TiO2 nanoparticles and disperse anatase TiO2 nanoparticles uniformly on the surface of rutile TiO2 powders. Rutile TiO2 powders coupled with anatase TiO2 nanoparticles are successfully prepared. Additionally, we compare the photocatalytic activity of these rutile-anatase coupled TiO2 powders under ultraviolet (UV) light and demonstrate that the reason for the improvement of photocatalytic activity is microstructural.