Diels-Alder click reaction was successfully applied for the preparation of 3-arm star polymers (A(3)) using furan protected maleimide end-functionalized polymers and trianthracene functional linking agent (2) at reflux temperature of toluene for 48 h. Well-defined furan protected maleimide end-functionalized polymers, poly (ethylene glycol), poly(methyl methacrylate), and poly(tert-butyl acrylate) were obtained by esterification or atom transfer radical polymerization. Obtained star polymers were characterized via NMR and GPC (refractive index and triple detector detection). Splitting of GPC traces of the resulting polymer mixture notably displayed that Diels-Alder click reaction was a versatile and a reliable route for the preparation of A(3) star polymer. (C) 2007 Wiley Periodicals, Inc.