Biochar reinforced advanced nanocomposites are of interest to a wide circle of researchers. Herein, we describe a novel MOF-derived reinforced cow dung biochar composite, which was prepared by a one-step hydrothermal method to form the MOF MIL-125(Ti) onto a nitrogen and sulfur co-doped bio-carbon (NSCDBC). The UV-vis diffuse reflectance spectrum of NSCDBC/MIL-125(Ti) exhibits an extension of light absorption in the visible region (360–800 nm), indicating its higher visible light capture capacity relative to pure MIL-125(Ti). The photocatalytic activity results show that all the NSCDBC/MIL-125(Ti) composite samples, namely NSCM-5, NSCM-10, NSCM-20 and NSCM-30 display good performance in the removal of tetracycline hydrochloride compared to pure MIL-125(Ti). Among them, NSCM-20 exhibits the highest catalytic activity with a removal rate of 94.62%, which is attributed to the excellent adsorption ability of NSCDBC and the ability to inhibit the complexation of photogenerated electron–hole pairs. Photoluminescence verifies that the loading of biochar successfully enhances the separation of photogenerated electron–hole pairs. Subsequently, the active species in the photocatalytic process are identified by using electron spin resonance spin-trap techniques and free radical trapping experiments. Finally, the possible reaction mechanism for the photocatalytic process is revealed. These results confirm that NSCDBC/MIL-125(Ti) is a potentially low-cost, green photocatalyst for water quality improvement.