We newly designed a functionalized monomer (PhAVE-AcOH) containing a phenylacetylene (PhA) group and a 1-(acetoxy)ethoxy group, the latter of which is expected to act as an initiator moiety in combination with Lewis acid-based activators under living cationic polymerization conditions. A polyPhA-based multifunctional initiator poly(PhAVE-AcOH) with a narrow molecular weight distribution (M w/M n = 1.02) was synthesized by Rh complex-mediated living coordination polymerization of PhAVE-AcOH. Then, living cationic graft polymerization of isobutyl vinyl ether (IBVE) was performed employing the pendant 1-(acetoxy) ethoxy initiating moiety of poly(PhAVE-AcOH) to form polyIBVE-grafted polyPhA(polyPhA-g-polyIBVE), where both the main chain and side chains possessed well-controlled structures (M w/M n = 1.05-1.10). We found that UV-vis absorption spectra of polyPhA-g-polyIBVE were progressively redshifted with increasing molecular weights of the graft chain.