Dendronized copolymers bearing two different dendrons as side chains have been synthesized using a modular orthogonal double-click reaction based strategy. The orthogonality of the Huisgen-type azide-alkyne cycloaddition and the Diels-Alder reaction was utilized to attach different dendrons to the polymer backbone via the graft-to strategy. First through third generations of polyaryl ether dendrons appended with an alkyne group and polyester dendrons possessing a furan-protected maleimide group at their focal point were reacted with a styrene based copolymer containing azide and anthracene moieties as side chains. The efficiency and selectivity of the orthogonal dendronization of the copolymers were examined via various analytical methods such as H-1 NMR spectroscopy, FTIR and gel permeation chromatography. (c) 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 5029-5037