The design and synthesis of novel charge (hole- or electron-) transport materials have been the focus of much research in recent years because of their wide variety of applications. In this study, three high molecular weight poly(arylene ether)s, 6a-c, containing naphthyl-substituted benzidine moieties have been synthesized from carbamates derived from bisphenols. After masking with n-propyl isocyanate, the carbamate is stable, can be readily purified by recrystallization from toluene, and can be polymerized directly with difluoro compounds under mild conditions. The resulting polymers possess high glass-transition temperatures, excellent thermal stability, and good film-forming properties. In comparison, the poly(arylene ether)s 6a'-c', synthesized from unprotected bisphenol, have lower molecular weights and wider polydispersity and contain some brown impurities. Preliminary experiments show that both 6a and 6a' can function well as hole-transport materials in light-emitting diodes.