π-Conjugated polymers are an attractive class of materials due to their potential applications in electronic devices, but the molecular weight and polymer end groups have not been preciously controlled because most of the polymers have been synthesized by typical step-growth condensation polymerization. However, living polymerization process in the synthesis of π-conjugated polymers has been recently attained by catalyst transfer condensation polymerization, in which the metal catalyst is transferred intramoleculary to the polymer end group of the elongated molecule. This highlight review provides the discovery and development of this polymerization method and its application to the synthesis of π-conjugated polymer architectures such as polymer brush and block copolymers.