The graft polymers [poly(isoprene)-graft-poly(styrene)] (PI-g-PS), [poly(isoprene)-graft-poly(isoprene)] (PI-g-PI), [poly(isoprene)-graft-(poly(isoprene)-block-poly(styrene))] PI-g-(PI-b-PS), and [poly(isoprene)-graft-(poly(styrene)-block-poly(isoprene))] PI-g-(PS-b-PI) with PI as main chain were synthesized through living anionic polymerization (LAP) mechanism and the efficient coupling reaction. First, the PI was synthesized by LAP mechanism and epoxidized in H2O2/HCOOH system for epoxidized PI (EPI). Then, the graft polymers with controlled molecular weight of main chain and side chains, and grafting ratios were obtained by coupling reaction between PI-Li+, PS-Li+, PS-b-PI-Li+, or PI-b-PS-Li+ macroanions and the epoxide on EPI. The target polymers and all intermediates were well characterized by SEC,1H NMR, as well as their thermal properties were also evaluated by DSC. (C) 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012