Well-defined polyacrylamide-polystyrene copolymers were grafted from the fibrillar clay, attapulgite, by a four-step self-assembly process: (i) the gamma-aminopropyltriethoxyl silane was self-assembled onto the surfaces of the attapulgite; (ii) the surface amino groups were amidated with bromoacetylbromide; (iii) the bromo-acetamide modified attapulgite was used as macro-initiator for the surface-initiated atom transfer radical polymerization of styrene with the catalyst of the complex of 1,10-phenanthroline and Cu(I)Br; (iv) the polystyrene grafted attapulgite was then used as macro-initiator for the polymerization of acrylamide. The two steps of the surface-initiated atom transfer radical polymerizations were all conducted under ultrasonic irradiation at room temperature. The product, polyacrylamide-polystyrene copolymers grafted attapulgite, had been characterized with elemental analysis, Fourier transform infrared spectroscopy, Thermogravimetric analysis (TGA), X-ray photoelectron spectroscopy, X-ray diffractometry, and transmission electron microscopy.