Atom transfer radical polymerization (ATRP) of styrene catalyzed by cuprous (CuX)/1,10-phenanthroline (Phen)and CuX/CuX2/Phen was conducted in an aqueous dispersed system. A stable latex was obtained by using ionic surfactant sodium lauryl sulfonate (SLS) or composite surfactants, such as SLS/polyoxyethylene nonyl phenyl ether (OP-10),SLS/hexadecanol and SLS/OP-10/hexadecanol. Among which SLS and SLS/OP-10/hexadecanol systems established better dispersed effect during the polymerization. It was found that Phen was a more suitable ligand than N,N,N,N",N"-pentamethyldiethylenetriamine (PMDETA) to maintain an appropriate equilibrium of the activator Cu(Ⅰ) and the deactivator Cu(Ⅱ) between the organic phase and the water phase. The effect of several initiators (such as EBiB, CCl4 and 1-PEBr) and the temperature on such a kind of ATRP system was also observed. The number-average molar mass (Mn) of polystyrene (PS)increased with the conversion and the molar mass distribution (Mw/Mn) remained narrow. These experimental data show that the polymerization could be controlled except for the quick increase of monomer conversion and the number-average molar mass of PS in the initial stage of polymerization. Furthermore, the initiator efficiency was found to be low (～57%) in CuX/Phen catalyzed system. To overcome this problem, Cu(Ⅱ )X2 (20 mol%-50 mol% based on CuX) was introduced into the polymerization system. In this case, higher initiator efficiency (60%-90%), low Mw/Mn of PS (as low as 1.08) were achieved and the molar masses of the PS fit with the theoretical ones.