Bifunctional alkoxyamine bis-TIPNO derived from 2,2,5-trimethyl-4-phenyl-3-azahexane-3-oxyl(TIPNO) and α, ω-alkyl bromide by atom transfer radical addition(ATRA) was employed as "biradical initiator" for nitroxide-mediated radical polymerization(NMRP) of isoprene and styrene. The kinetics study for the polymerization of styrene at different time showed living features. The poly(styrene-b-isoprene-b-styrene)(SIS) copolymers have two glass transition temperatures, indicating the immiscibility of the corresponding blocks.