In this paper, we used a facile ball milling, microwave radiation and heating treatment method to achieve the surface modification of TiO2 with low g-C3N4 concentration, and a multilayer heterojunction composite with TiO2 as the main part and g-C3N4 as the modification agent was obtained. The obtained materials were analyzed by several characterizations to get information on their chemical composition, crystalline structure, vibrational features and optical properties. The photocatalytic performance was evaluated by degradation of rhodamine B (RhB) and methylene blue (MB) under UV, visible and direct solar light irradiation. Its photocatalytic activity was enhanced depended on the novel structure of g-C3N4/TiO2 hybrid and the special Z-scheme electron-hole transfer model of multilayer heterointerfaces. The material preparation and structural features could be useful for the design and development of other photocatalysts with high photocatalytic activity.