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• A novel CoAl-LDH/Bi 12 O 17 Cl 2 (x-LB) photocatalyst was prepared for the first time. • Optimal 5-LB exhibited high photocatalytic activity for CIP and BPA degradation. • h+ and 1O 2 serve as main reactive species for the photocatalytic degradation of CIP. • The application of 5-LB in real water matrices and natural sunlight was studied. • Nontoxicity of 5-LB and the treated CIP validated the application potential. The widespread distribution of persistent organic pollutants (POPs) in natural waters has aroused global concern due to their potential threat to the aquatic environment. Photocatalysis represents a promising mean to remediate polluted waters with the simple assistance of solar energy. Herein, we fabricated a Co-Cl bond reinforced CoAl-LDH/Bi 12 O 17 Cl 2 heterogeneous photocatalyst to investigate the feasibility of photocatalysis to treat POPs-polluted water under environmental conditions. The optimum CoAl-LDH/Bi 12 O 17 Cl 2 (5-LB) composite photocatalyst exhibited excellent photocatalytic performance, which could degrade 92.47 % of ciprofloxacin (CIP) and 95 % of bisphenol A (BPA) with 2h of actual solar light irradiation in Changsha, China (N 28.12 °, E 112.59 °). In view of the synergistic influence of water constituents, various water matrices greatly affected the degradation rate of CIP (BPA), with the degradation efficiency of 82.17% (84.37%) in tap water, 69.67% (71.63%) in wastewater effluent, and 44.07% (67.7%) in wastewater inflow. The results of electron spin resonance, and chemical trapping experiment, HPLC-MS and density functional theory calculation reflected that the degradation of CIP was mainly attributed to h+ and 1O 2 attacking the active atoms of CIP molecule with high Fukui index. Furthermore, the non-toxicity of both 5-LB photocatalyst and treated CIP solution was proved by E.coli and B.subtilis cultivation, which further demonstrated the feasibility of the 5-LB to treat POPs in real water under irradiation of solar light. [Display omitted] [ABSTRACT FROM AUTHOR]