The dendrimer-like copolymers [PEEGE-(PS/PEO)](n) (n >= 2) based on the star[Polystyrene-Poly(ethylene oxide)-Poly(ethoxyethyl glycidyl ether)] Estar(PS-PEO-(PEEGE-OH))] terpolymers were synthesized by click chemistry. First, the star-shaped copolymers star[PS-PEO-(PEEGE-Alkyne)] (also termed as [PEEGE-(PS/PEO)](1)) were synthesized by the reaction of hydroxyl end group at PEEGE arm (on star[PS-PEO-(PEEGE-OH)]) with propargyl bromide. Then, the small molecule 1,4-diazidobutane (DAB) with two azide groups and pentaerythritol tetrakis (2-azidoisobutyrate) (PTAB) with four azide groups were synthesized and reacted with [PEEGE-(PS/PEO)](1) by the click chemistry for dendrimer-like [PEEGE-(PS/PEO)](2) and [PEEGE-(PS/PEO)](4), respectively. However, in the latter case, only the [PEEGE-(PS/PEO)](3) was formed as the main product because of the steric effect. The final dendrimer-like [PEEGE-(PS/PEO)](n) copolymers were characterized by SEC and H-1-NMR in detail. Comparing with the SEC of their precursor [PEEGE-(PS/PEO)](1), the curves of [PEEGE-(PS/PEO)](2) was shifted to the shorter elution time, while that of [PEEGE-(PS/PEO)](n) (n >= 3) was shifted to the longer elution time, which was attributed to the different hydrodynamic volume derived from their separate structures and compositions in THF solution. (C) 2009 Wiley Perio dicals, Inc. J Polym Sci Part A: Polyrn Chem 47: 4800-4810, 2009