Two new homologous series of 4-cyano- and 4-nitro-N-(4-alkoxysalicylidene) anilines were synthesized. The phase transitions of these homologues were determined by using a differential scanning calorimeter and an ordinary polarizing microscope. It is shown that all the homologues having a terminal cyano group exhibit a nematic phase. The members with a nitro substituent exhibit a mesomorphic phase as the terminal alkoxyl chain is increased. The homologues of these two homologous series having an alkoxyl chain longer than heptyloxy show a smectic A phase. Furthermore, it is indicated that some members of these homologous series exhibit a photochromic property in the solid state.