We have developed a living anionic polymerization of 4-vinyltriphenylamine (VTPA) in tert-butylbenzene at 25 degrees C or tetrahydrofuran at -78 degrees C initiated with sec-butyllithium in the absence of any additives based on a high-vacuum (10(-6) Torr) technique. Lithium naphthalenide could also initiate the polymerization of VTPA to generate difunctional living PVTPA. The molecular weights of poly(VTPA) (PVTPA) were proportionally increased up to around 30 K by increasing the feed ratio of VTPA to the initiator, while keeping very low polydispersities (PDIs) of less than 1.1. A new series of block copolymers, PVTPA-b-poly(methyl methacrylate) and polystyrene (PS)-b-PVTPA-b-PS, have been successfully synthesized by exploiting the living nature of PVTPA. We were also successful in synthesizing novel and optoelectrically active coil-rod-coil triblock copolymers comprised of regioregular poly(3-hexylthiophene) (P3HT) and PVTPA segments. Their characterization as well as thermal and optical properties have been investigated. Furthermore, the self-assemble behavior of the block copolymers displaying periodic nanostructures has been confirmed by atomic force microscopy and transmission electron microscopy.