A homologous series of cholesteryl ω-phenylalkanoates was synthesized from cholesterol and the imidazolides of ω-phenylalkanoic acids. The mesomorphic properties of 16 members, cholesteryl benezoate through cholesteryl 16-phenylhexadecanoate, were determined microscopically. All homologues, except cholesteryl phenylacetate, show a cholesteric mesophase. A monotropic smectic mesophase is found in cholesteryl 8-phenyloctanoate, 10-phenyldecanoate and higher members. The values of the cholesteric-isotropic transition temperatures alternate with increasing chain length, but the smectic-cholesteric transition temperatures do not show this odd-even effects. Cholesteric colors are exhibited by most of the cholesteryl ω-phenylalkanoates and a well-defined visible spectrum of selectively reflected light by cholesteryl 10-phenyldecanoate and successive homologues.