Efficient charge separation and cycle stability are critical for water purification by semiconductor photocatalyst. Herein, novel Ag2S/AgVO3 graphene aerogels (Ag2S/AgVO3@GAs) were synthesized via an in situ ion exchange method. The series of characterization results verified that the Ag2S/AgVO3@GAs synergistically integrate the excellent properties of the Ag2S and AgVO3 into the macroscopic porous graphene aerogel. Furthermore, owing to the chelation of chitosan (CS) for AgVO3 and the ion exchange between well-dispersed AgVO3 and Na2S, the Ag2S can in situ grow on AgVO3, which prevents Ag2S and AgVO3 agglomeration/shedding in the photocatalytic reaction and contributes to the enhanced photocatalytic activity and cyclic stability. Benefiting from the unique structure, the Ag2S/AgVO3@GAs with excellent stability displayed the outstanding photodegradation efficiency for methyl orange (97% removal rate in 40 min) and disinfection activity for Escherichia coli (100% antibacterial efficiency in 36 min).