A novel 2D visible-light-driven TiO2@Ti3C2/g-C3N4 ternary heterojunction photocatalyst with modified interfacial microstructure and electronic properties was synthesized by ultrasonic-assisted calcination method. The remarkably active g-C3N4 could provide high productivity of photogenerated electrons and holes. Meanwhile, the O/OH-terminated Ti3C2 and by-product TiO2 could act as excellent supporters by migrating electrons in TiO2@Ti3C2/g-C3N4 hybrids. As a result, the highest photocatalytic activities in the degradation of aniline and RhB were increased to 5 and 1.33 times higher than that of pristine g-C3N4 under visible-light irradiation, respectively. Furthermore, we proposed that n-n heterojunction and n-type Schottky heterojunction were built up across their interfaces, which efficiently improve the transition of electrons and further promote the photocatalytic activity of TiO2@Ti3C2/g-C3N4 hybrids. More appealingly, all the results highlight that the environment-friendly TiO2@Ti3C2/g-C3N4 heterojunction hybrids would be desirable candidates for pollutants degradation.