The synthesis of poly{2,5-bis[(4-methoxyphenyl)oxycarbonyl]styrene} (PMPCS) with different molecular weight and low polydispersity was achieved by atom transfer radical polymerization in methoxybenzene solution using 1-bromoethylbenzene as an initiator and CuBr/sparteine complex as a catalyst. The concentration of the living centers throughout the polymerization was found to be constant. The liquid-crystalline behavior of the polymers with M-n ranging from 3800 to 17,400 g/mol was studied using DSC and POM. Only the polymers with M-n beyond 10,200 g/mol formed a liquid-crystalline phase, which was quite stable with a high clearing point (higher than the decomposition temperature of the polymer).