Ternary Ag/Ag2S/Ag3CuS2 hollow microspheres were synthesized via an in situ ion-exchange method using Cu7S4 hollow submicrospheres as the template. The as-obtained Ag/Ag2S/Ag3CuS2 composite exhibited a well-defined uniform hollow microsphere morphology with an average diameter of about 1.3 μm. The photocatalytic property of the as-prepared Ag/Ag2S/Ag3CuS2 hollow microsphere composite was investigated by the decomposition of methyl orange (MO) under visible light irradiation (λ > 420 nm). It was shown that the photocatalytic activity of the Ag/Ag2S/Ag3CuS2 hollow microsphere was higher than those of Ag/Ag2S, Cu2O, Cu7S4 and P25 for the photodegradation of MO under visible light irradiation. Radical scavenger experiments demonstrated that superoxide radicals and holes were the main reactive species for MO degradation.