For the first time, hydrozirconation and halogenolysis of 1,2-polybutadiene (1,2-PBD, by living anionic polymerization) were studied to synthesize reactive poly-halohydrocarbons, which provide a platform for preparing well-defined functional polymers via macromolecular substitution. Hrirozirconation and halogenolysis afforded quite convenience for anti-Markovnikov hydrohalogenation of 1,2-PBD with controllable degree of functionalization. Diverse functional polymers and branched polymers were synthesized after macromolecular substitution reaction with a broad range of commercially available nucleophiles (amines, phenols, alcohols, carbanions, carboxylates, and azide) or macromolecular nucleophiles. NMR and GPC characterizations confirmed high conversion in substitution reaction and narrow molecular weight distribution of the resultant functional polymers, respectively. The methodology utilizing Schwartz's reagent for hydrozirconation of macromolecules could greatly facilitate the modification of vinyl groups containing polymers with high efficiency.