A series of rod-coil diblock copolymers, consisting of poly{2,5-bis[(4-methoxy-phenyl)oxycarbonyl]styrene} as a rigid segment and poly(n-butyl acrylate) as a flexible part, were successfully prepared through two inverse procedures by atom transfer radical polymerization. The copolymers were characterized by H-1 NMR and gel permeation chromatography and had high molecular weights and relatively narrow polydispersities (polydispersity index < 1.20). All the block copolymers synthesized had two distinct glass-transition temperatures according to differential scanning calorimetry. A polarizing optical microscopy investigation demonstrated the liquid crystallinity of the diblock copolymers. The self-assembly behaviors in dilute solutions was studied by transmission electron microscopy. (c) 2005 Wiley Periodicals, Inc.