Synthesis and physico-chemical properties of 4-alkoxyphenyl and 4-alkoxybiphenyl-4'-yl 2H-pyran-2-one-5-carboxylates, 2H-chromen-2-one-6-yl 4-alkoxybenzoates and 4-alkoxybiphenyl-4'-carboxylates, and 2H-chromen-2-one-7-yl 4-alkoxybenzoates and 4-alkoxybiphenyl-4'-carboxylates are described. Terminal 2H-pyran-2-one and chromen-2-one cores are effective in enhancing liquid crystalline properties. The layer structure was examined by a small angle X-ray measurement, and the results are discussed in terms of the molecular structure. The polar effect of the terminal lactone group is recognized in the thermal properties and the layer structure of smectic A (SmA) phase.