BiOCl/graphene aerogel graphene (BGA) was successfully obtained by in situ hydrothermal synthesis, and the chemical, structural, morphological, and photocatalytic properties were systematically characterized. BGA with the doping amount of BiOCl at 20% (BGA-4) exhibited the optimal activation efficiency for persulfate (PDS) on the degradation of methyl orange (MO) under simulated sunlight (SSL) illumination as compared to the pure graphene (GA) and aerogel composites with different BiOCl content. The influence of various reaction parameters on the MO removal efficiency, such as the reaction system, catalyst activator dose, PDS concentration, BiOCl doping amount, and the initial pH of the solution, was investigated. Under optimum conditions, the catalytic efficiency of BiOCl-doped GA with the mass ratio of 20% (BGA-4) was 5.61 times that of GA. The strengthening effect of BGA-4 benefited from the synergistic effect of1O2, O2·−and the generation and rapid electron transfer of photo-induced electron (e−) in the BGA-4/SSL/PDS system. Considering the superior stability and recyclability of BGA-4, the BGA-4/SSL/PDS system exhibits great potential in actual wastewater treatment.