The strategy to improve the photocatalytic removal efficiencies towards organic pollutants is still a challenge for the novel Sillen–Aurivillius perovskite type Bi4NbO8Cl. Herein, we report carbon-supported TiO2/Bi4NbO8Cl (C-TiO2/Bi4NbO8Cl) heterostructures with enhanced charge separation efficiency, which were fabricated via molten-salt flux process. The carbon-supported TiO2 particles were derived from MXene Ti3C2 precursors, and attached on plate-like Bi4NbO8Cl, acting as electron-traps to achieve supressed recombination of photo-induced charges. The improved charge separation confers C-TiO2/Bi4NbO8Cl heterostructures superior photocatalytic performance with 53% higher than pristine Bi4NbO8Cl, towards rhodamine B removal with the help of photo-induced holes. Moreover, the C-TiO2/Bi4NbO8Cl heterostructures can be expanded to deal with other water contaminants, such as methyl orange, ciprofloxacin and 2,4-dichlorophenol with 44, 25 and 13% promotion, respectively, and thus the study offers a series of efficient photocatalysts for water purification.