In-situ oxygen vacancy-mediated C-N-S-tridoped single crystal black TiO2(B) nanorods are smoothly manufactured. The sample preparation is divided into two steps, first of all, a simple hydrothermal process, followed by an in-situ solid-state chemical substitution method with calcination at 500 degrees C. We have a number of representations of the catalyst such as crystallinity, morphological structure, etc. by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy, and UV-vis diffuse reflectance spectroscopy, respectively. This b-C-N-S-TiO2(B) has the advantages of Oxygen Vacancy, single crystal structure of nanorods, Ti3+ self-doping, C-N-S-tridoped, so this sample band gap is narrow. Moreover, through the reduction of phenol and Cr(VI), we know the photocatalytic performance of the b-C-N-S-TiO2(B), the reduction efficiency of phenol and Cr(VI) is similar to 6.1 times and similar to 7 times of no doping samples, respectively, under visible light illumination. The predominant photocatalytic performances because of the synergetic action of Ti3+ self-doping, C-N-S-tridoped, oxygen vacancy, and the 1D single crystal B phase nanostructure, favoring the separation and transportation of photogenerated charge carriers and the visible light utilization.