Well-defined ambipolar block copolymers containing carbazole, oxadiazole moieties, and only one homoleptic iridium(III) complex between the carbazole and oxadiazole blocks were successfully synthesized by sequential living anionic polymerization with controlled molecular weights (Mw), a narrow molecular weight distribution (Mw/Mn < 1.15), and a high conversion yield (98-100%). The optimum conditions for the successful controlled synthesis of an oxadiazole-containing the homopolymer of poly(2-phenyl-5-(6-vinylpyridin-3-yl)-1,3,4-oxadiazole) have been established by controlling the nucleophilicity strength of the carbanion. In addition, the location and concentration of the homoleptic iridium(III) complex were controlled by linking it to 1,1-diphenylethylene, which exhibits monoaddition characteristics in the main chain of the block copolymer.