The highly ordered silver-coated colloidal crystals arrays and macroporous silver films were derived through an electrostatics-induced adsorption effect using polystyrene(PS) as templates. Carboxyl-modified PS microspheres were prepared by emulsifier-free emulsion polymerization using methacrylic acid(MAA) as the functional monomer. PS microspheres were self-assembled into close packing colloidal crystals of facecentered cubic arrays to the substrate with vertical deposition method. These colloidal crystals were modified using dopamine(DA) to form poly-dopamine(PDA) during its oxidative polymerization. Through electrostatic interaction, the silver nanoparticles were deposited and adsorbed onto the surfaces of colloidal crystals templates by exposing [Ag(NH_3)_2]^+solution to infrared irradiation. Removal of the polymeric template by etching with methylbenzene solvent resulted in 3D ordered macroporous silver films. The structural and properties of the ordered silver-coated arrays and macroporous silver films were characterized by field emission scanning electron microscopy(FE-SEM), X-ray diffraction(XRD), UV-vis spectroscopy and surface-enhanced Raman spectroscopy(SERS). The results indicate that the prepared silver-coated arrays and macroporous silver films possess the features of ordered multilayer arrangement, uniformity and repeatability as well as an ideal SERS effect.