• Bi 2 WO 6 / Natural hematite was utilized as a heterogeneous catalyst for PMS activation. • BW/NH catalyst exhibited excellent performance for the degradation of TC, OFX, AMX, SMZ and MNZ. • The synergistic effect in the BW/NH/PMS/Vis system produced SO 4 − and OH reactive species. • The possible degradation pathways of OFX were proposed via HPLC-MS. Natural hematite (α-Fe 2 O 3 ) serving as a potential Fenton/Fenton-like reagent can be applied in advanced oxidation processes (AOPs) for wastewater treatment. Considering the fast charge carrier recombination of natural hematite, Bi 2 WO 6 /natural hematite (BW/NH) heterojunctions were successfully synthesized for highly efficient photo-Fenton-like peroxymonosulfate (PMS)-based advanced oxidation processes. The heterojunction catalysts exhibited high activity and stability in activating PMS to generate radicals ( OH, SO 4 − ) for the removal of various antibiotics under visible light with comparable degradation ratios, including tetracycline hydrochloride (TC, 91%), ofloxacin (OFX, 94%), amoxicillin trihydrate (AMX, 100%), sulfamethoxazole (SMZ, 72%) and metronidazole (MNZ, 89%). The pseudo-first-order reaction constants of BW/NH/PMS/Vis system in the photo-Fenton-like system were 7.77 and 1.95 times of BW/NH/Vis and BW/NH/PMS system, respectively. Moreover, BW/NH/PMS/Vis system obtained TOC removal efficiencies of 67.44% (TC), 75.53% (OFX), 78.96% (AMX), 62.34% (SMZ) and 59.62% (MNZ) within 200 min. Furthermore, the main reactive oxidant species were studied and possible degradation pathways of OFX as well as enhanced mechanisms of the photo-assisted Fenton-like system were proposed. This work provides new insights that the synergistic effect of Fenton-like processes and photocatalysis with the utilization of natural minerals holds broad prospects for environment remediation.