A polymer having a trithiocarbonate moiety in its main chain was synthesized with a cyclic, five-membered dithiocarbonate as a building block. The trithiocarbonate in the polymer acted as a reversible addition-fragmentation chain transfer reagent to mediate a controlled insertion polymerization of styrene into the polymer main chain, giving the corresponding sequence-ordered polymer having a well-defined polystyrene segment in the main chain. During the polymerization, the polystyrene segment in the main chain gained its molecular weight, which maintained a linear relationship with the conversion of styrene. The insertion polymerization of styrene was induced not only thermally but also by ultraviolet irradiation. This photoinduced polymerization was well controlled by the trithiocarbonate moiety to give the corresponding polymer, whose structure was virtually the same as that obtained by the thermal polymerization. (c) 2006 Wiley Periodicals, Inc.