New AB diblock copolymer in-chain anions having poly(2-vinylpyridine) (P2VP) and/or poly(methyl methacrylate) (PMMA) blocks, whose anion is located at the junction between the A and B blocks, have been prepared by the 1:1 addition reaction of the living polymer (A) with the omega- or alpha-terminal 1-phenyl1-( 2-pyridinyl) ethylene-functionalized polymer (B). The P2VP-block-PS, PS-block-P2VP, P2VP-blockpoly( 4-tert-butyldimethylsilyloxystyrene), PS-block-PMMA, and P2VP-block-PMMA in-chain anions could be practically prepared for the first time. Based on this preparation, a newly synthesized 1,4-bis(1-(2pyridinyl) ethenyl) benzene satisfactorily works as a key core agent, with which the polymers (A) can be connected to the polymer (B), and the in-chain anion can be generated between the A and B polymers. By developing the iterative methodology with such new block copolymer in-chain anions as the building blocks, the successive synthesis of the 3-arm ABC and 5-arm ABCDE mu-star polymers having PMMA and P2VP arms, which were synthetically difficult by the previous systems, have been successfully achieved. The success of the developed methodology demonstrates the further possibility to synthesize more component mu-star polymers. (C) 2017 Elsevier Ltd. All rights reserved.