A new type of macroinimers were synthesized by the capping reaction of hydroxyl groups of polyazoesters with isocyanato ethyl, methacrylate in the presence of dibutyl tin dilaurate. Macroinimers having PEG-400 and PEG-1500 units were used in the polymerization of methyl methacrylate (MMA) or styrene (S) to obtain PS-PEG or PMMA-PEG branched block copolymers at 60°C. Longer polymerization times or higher macroinimer concentrations led to cross-linked block copolymers. Similarly neat homopolymerization of macroinimers also led to the cross-linked polyethyleneglycols. The products were characterized by IR and NMR spectroscopy, viscosity measurements and fractional precipitation.