Poly(divinylbenzene-co-acrylic acid) (poly(DVB-co-AA)) hollow microspheres with gold nanoparticles on the interior surfaces were prepared from the gold nanoparticles-coated poly(methacrylic acid) (PMAA@Au@poly(DVB-co-AA)) core-shell microspheres by removal of the PMAA core in water. Au nanoparticles-coated PMAA microspheres were afforded by the in-situ reduction of gold trichloride with PMAA microsphere as stabilizer via the interaction between carboxylic acid groups and Au nanoparticles. Gold nanoparticles-coated (PMAA@Au@poly(DVB-co-AA)) microspheres were formed during the distillation precipitation copolymerization of divinylbenzene and acrylic acid in acetonitrile with Au-coated PMAA microspheres as seeds. The thickness of the poly(DVB-co-AA) shell-layer was controlled by the amount of the solvent distilled off the polymerization system. The PMAA microspheres, Au nanoparticles-coated PMAA microspheres, core-shell microspheres, and hollow microspheres with Au nanoparticles on the interior surfaces were studied by transmission electron microscopy and scanning electron microscopy. The stabilization to L-cysteine and the preliminary catalytic property of the Au nanoparticles on the inner surface of hollow poly(DVB-co-AA) microspheres were investigated.