Several new alkyl pyridinium salts, namely 1-n-alkyl-4-cyanopyridinium bromides with alkyl chains containing 14, 16, and 18 carbon atoms, were synthesized, and their mesomorphic and micellar properties were studied. For compounds with 16 and 18 carbons in the alkyl chain, a thermotropic smectic A phase is present. The compounds also behave as surfactants in dilute aqueous solutions, and the Krafft temperature and the critical micelle concentration of each compound were determined.