The surface grafting of attapulgite (ATP) with polystyrene (PS) was established via a simultaneous reverse and normal initiation atom transfer radical polymerization (SR&NIATRP). 4-(chloromethyl)phenyltrimethoxysilane (CMPTMS) chemical bounded on the surface of ATP (ATP-Cl, Cl-I) was prepared via one-step self-assembly. SR&NI ATRP of styrene was conducted using CuCl2 complex tris(2-(dimethylamino)ethyl)amine (Me-6-TREN) as the catalytic system, initiated by 2,2-azobis(isobutyronitrile) (AIBN) and ATP-Cl. FT-IR, XRD, XPS, TGA and TEM data were consistent with the grafting of benzyl chloride groups and PS chains on ATP surface. The controllability of polymerization was investigated by the kinetics behavior under different molar ratio of AIBN and CuCl2. The obtained polymer possessed a uniform distribution of molecular weights with a lower polydispersity index of 1.2 similar to 1.4. The relationship between polymerization on the surface of ATP and in solution was discussed in detail based on TGA data of hybrid particles and GPC trace of free polymer in solution. (C) 2015 Wiley Periodicals, Inc.