Heterogeneous photocatalysis namely titanium dioxide supported on reed straw biochar (acid pre-treated) (TiO/pBC) was synthesized by sol-gel method. The morphology, surface area and structure of TiO/pBC were characterized by scanning electron microscopy (SEM), Brunauer-Emmett-Teller (BET), and X-ray diffraction (XRD). Low calcination condition maintained the structure of biochar completely and prevented the agglomeration of TiO particles. Due to the combination of adsorption and photocatalysis, TiO/pBC performed higher removal efficiency of sulfamethoxazole (SMX) than pure TiO powder under UV light irradiation. The photocatalytic degradation (PCD) of SMX was also studied with the water collected from the Yellow River. Three high concentration inorganic anions (Cl, NO, SO) of the river exerted certain degree of detrimental effects on the contaminant degradation. TiO/pBC showed stable photocatalytic activity after five sequential PCD cycles. The biochar was able to promote further PCD on TiO by adsorbing SMX and intermediates thereby prolonging the separation lifetime of electrons (e) and valence band hole (h). The transformation intermediates of SMX were identified and three possible degradation reactions of hydroxylation, opening of isoxazole ring and cleavage of SN bond might occur during the PCD of SMX.