Diblock copolymers comprising crystallizable poly (c-caprolactone) and poly {2,5-bis[(4-methoxyphenyl)oxycarbonyl]styrene} (PMPCS) were synthesized by ring-opening polymerization of F-caprolactone and subsequent atom transfer radical polymerization (ATRP) of MPCS. The molecular structure of the copolymers was confirmed by H-1 NMR spectroscopy and GPC. Kinetic study of ATRP showed that the polymerization proceeded in a controlled way up to high conversions. Three series of diblock copolymers were obtained with relatively narrow polydispersity indices (PDI <= 1.11) and PCL blocks of 8000, 12,900, and 22,800 molecular weights, respectively. The existence of microphase separation was identified by differential scanning calorimetry (DSC) and directly observed through transmission electron microscopy (TEM). The melting behavior of PCL block was significantly affected by the length of PCL block and composition of PMPCS. The thermotropic liquid crystalline behavior was examined by polarized optical microscopy (POM) and DSC. The result showed that the diblock copolymer exhibited liquid crystalline behavior when the degree of polymerization (DP) of PMPCS block was not less than 44. (c) 2005 Elsevier Ltd. All rights reserved.