Side-chain liquid-crystalline polymers of 6-[4-(4'-methoxyphenyl)phenoxy]-hexyl methacrylate with controlled molecular weights and narrow polydispersities were prepared via reversible addition-fragmentation chain transfer (RAFT) polymerization with 2-(2-cyanopropyl) dithiobenzoate as the RAFT agent. Differential scanning calorimetry studies showed that the polymers produced via the RAFT process had a narrower thermal stability range of the liquid-crystalline mesophase than the polymers formed via conventional free-radical polymerization. In addition, a chain length dependence of this stability range was found. The generated RAFT polymers displayed optical textures similar to those of polymers produced via conventional free-radical polymerization. (C) 2003 Wiley Periodicals, Inc.