Hollow spheres of multicomponent (CuIn)(x)Zn(2(1-x))S2 solid solutions have been rapidly synthesized by a salt-assisted aerosol decomposition method. (CuIn)(0.2)Zn(1.6)S2 hollow spheres with a band gap of 2.53 eV exhibited an excellent and stable photocatalytic activity of 360 μmol h(-1) (50 mg photocatalysts) for hydrogen evolution from aqueous solutions containing sacrificial reagents (SO3(2-) and S(2-)) under visible light (λ≥ 420 nm) due to the well-crystallized microspheres and mesoporous structures. H2 evolution rate of the (CuIn)(0.2)Zn(1.6)S2 hollow spheres reached as high as 57 μmol h(-1) (50 mg photocatalysts) even without Ru loading.