We demonstrate the use of a supernormal valence transition-metal (Ce(IV) and Cu(III))-mediated redox system for the surface grafting on the halloysite nanotubes (HNTs). Following this way, commonly-used vinyl monomers were grafted on HNTs in one step under mild condition. The grafting was evidenced using FTIR, X-ray photoelectron spectroscopy (XPS), and thermogravimetric analysis (TGA). The micromorphology was carefully characterized by transmission electron microscope (TEM). The results indicate that the surface grafting reaction was successfully processed in all cases, in which the Ce(IV) shows a much higher initiation activity than that of Cu(III). Then a uniform hydrogel was constructed by mixing poly(triethyl(4-vinylbenzyl)phosphonium chloride-grafted HNTs (HNTs-P(Et-P)) with sodium polyacrylate-grafted HNTs (HNTs-P(AA-Na)), which show desirable antibacterial activity.