||Although nickel catalysts are stable, highly active, and have been shown good controllability in the polymerization of phenylisocyanides, it is limited to the electron-poor phenylisocyanides. Herein, we achieved the living polymerization of not only electron-poor but also electron-rich phenylisocyanides using the nickel (II) complexes. The key to the successful living polymerization was the high stability on the chain-end because of tightly bound chelating ligand. Various phenylisocyanides underwent living polymerization to give a linear increase in Mn upon changing the M/I ratio and narrow polydispersity indices (PDIs). In addition, we confirmed that the electronic character of the monomer have a significant effect on the polymerization efficiency. Furthermore, we achieved the synthesis of pentablock copolymer containing various substituents from electron-withdrawing to electron-donating group only in a minute.