Rational design and synthesis of graphene-based photoactive heterostructures is in great demand for various applications. Herein, a novel microporous amorphous-ZnO@TiO2/graphene heterostructure was developed via a facile approach for the first time. This heterostructure possesses excellent characteristics such as high surface area (336 m(2) g(-1)), excellent mobility of charge carriers, and enhanced photocatalytic activity. The higher photocatalytic activity of the developed novel microporous amorphous-ZnO@TiO2/graphene hybrid was demonstrated through the degradation of water pollutants, MB and RhB. The mechanistic analysis result shows that the numerous unsaturated sites on the surface of amorphous-ZnO@TiO2 facilitate the separation of photogenerated electrons and holes, and graphene mainly acts as an electron transfer bridge. The combination of amorphous-ZnO@TiO2 and graphene constructs a new class of photocatalysts and also has a synergistic effect on improving the photocatalytic activity. The resultant amorphous-ZnO@TiO2/graphene ternary nanocomposite as a novel high performance photocatalyst is of a great potential for water pollution treatment due to its high catalytic activity, low cost, long-term stability, and easy recovery.