C3N4/TiO2 hybrid photocatalysts with highly enhanced photocatalytic performance were prepared by a facile ball milling method. A layered structure of g-C3N4 was formed on the surface of TiO2. The mechanochemical process can promote the dispersion of C3N4 on the surface of TiO2 particles, to form a single layer hybrid structure and a multi-layer core-shell structure. The photocatalytic activities of C3N4/TiO2 under visible and UV light irradiation were 3.0 and 1.3 times those of pure g-C3N4 and TiO2, respectively. Under visible light and UV irradiation, the photocurrent response was up to 2.5 times and 1.5 times as high as that of the pure TiO2 and C3N4, respectively. The evident performance enhancement of g-C3N4-TiO2 was mainly attributed to high separation and migration efficiency of electron-hole pairs.