Oxygen Vacancy (OVs) and carbon doping of the photocatalyst body will significantly enhance the photocatalytic efficiency. However, synchronous regulation of these two aspects is challenging. In this paper, a novel C@TiO2‐x photocatalyst was designed by coupling the surface defect and doping engineering of titania, which can effectively remove rhodamine B (RhB) and has a relatively high performance with wide pH range, high photocatalytic activity and good stability. Within 90 minutes, the photocatalytic degradation rate of RhB by C@TiO2‐x (94.1 % at 20 mg/L) is 28 times higher than that of pure TiO2. Free radical trapping experiments and electron spin resonance techniques reveal that superoxide radicals (⋅O2−) and photogenerated holes (h+) play key roles in the photocatalytic degradation of RhB. This study demonstrates the possibility of regulating photocatalysts to degrade pollutants in wastewater based on an integrated strategy.