Poly(benzyl ether)-b-polystyrene dendritic-linear polymers were successfully synthesized using a dendritic chloric poly(benzyl ether) (G(1)-Cl, G(2)-Cl, and G(3)-Cl) as the macroinitiator through the atom transfer radical polymerization process. The structure and properties of the resultant polymers were characterizated by gel permeation chromatography, H-1-NMR, Fourier transform IR, thermogravimetric analysis, and differential scanning calorimetry. It was found that the temperature, reaction time, molar ratio of the macromitiator to styrene, and the generation number of the macroinitiator have significant effects on the molecular weights, conversion, and polydispersities of the resulting polymers. These dendritic-linear block polymers had very good solubility in common organic solvents at room temperature. The terminal group (dendritic segments) of the polymers can affect their thermal stability. These dendritic-linear polymers after self-assembling in selective solvents (chloroform/acetone) formed core-shell micelles. (c) 2005 Wiley Periodicals, lnc.