Five A-B-A′, A-C-A′, B-A-B′, C-A-C′, and C-B-C′ triblock terpolymers with block orders difficult to synthesize by sequential polymerization have been successfully synthesized by a new methodology combining living anionic polymers with a specially designed linking reaction using α-phenylacrylate as the reaction site. Here, A(A′), B(B′), and C(C′) represent groups of polymers (having chain-end anions with different nucleophilicities), which are only polymerizable from A(A′) to B(B′) to C(C′) via sequential polymerization. The corresponding polymers are polystyrene (A) and poly(α-methylstyrene) (A′), poly(2-vinylpyridine) (B) and poly(4-vinylpyridine) (B′) and polymers from methacrylate type monomers like poly(methyl methacrylate) (C), poly(tert-butyl methacrylate) (C′), poly(2-hydroxyethyl methacrylate) (C′), poly(2,3-dihydroxypropyl methacrylate) (C′), and poly(ferrocenylmethyl methacrylate) (C′). Furthermore, three synthetically difficult B-A-B, C-A-C, and C-B-C triblock copolymers with molecular asymmetry in both side blocks have also been synthesized by the developed methodology. All of the polymers thus synthesized are quite new triblock terpolymers and copolymers with well-defined structures, i.e., precisely controlled molecular weights, compositions and narrow molecular weight distributions (Mw/Mn ≤ 1.05).