A series of novel comb polymers, poly{2,5-bis[(4-methoxyphenyl)oxycarbonyl]styrene}-g-polystyrene (PMPCS-g-PS), with mesogen-jacketed rigid side chains were synthesized by the grafting onto method from a-yne-terminated PMPCS (side chain) and poly(vinylbenzyl azide) (backbone) by Cu(I)-catalyzed 1,3-dipolar cycloaddition click reaction. The a-yne-terminated PMPCS was synthesized by Cu(I)-catalyzed atom transfer radical polymerization initiated by a yne-functional initiator. Poly(vinylbenzyl azide) was prepared by polymerizing vinylbenzyl chloride using nitroxide mediated radical polymerization to obtain poly(vinylbenzyl chloride) as the precursor which was then converted to the azide derivative. The chemical structure and architectures of PMPCS comb polymers were confirmed by 1H NMR, gel permeation chromatography, and multiangle laser light scattering. Both surface morphologies and solution behaviors were investigated. Surface morphologies of PMPCS combs on different surfaces were investigated by scanning probe microscopy. PMPCS combs showed different aggregation morphologies when depositing on silicon wafers with/without chemical modification. The PMPCS comb polymers transferred to polymer-modified silicon wafers using the Langmuir-Blodgett technique showed a worm-like chain conformation. (C) 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012