New liquid crystalline series with -methoxyethyl terminal chains have been prepared, -methoxyethyl 4-(4-n-alkoxybenzylideneamino)benzoate. In series, all the twelve synthesized compounds exhibit mesomorphism. Methoxy to n-hexadecyloxy derivatives exhibit enantiotropic smectic A mesophase. The nematic mesophase commences from n-methoxy derivative as an enantiotropic and persists up to the n-butyloxy homologue synthesized. All the homologues prepared were found to be enantiotropicallymesogenic and were screened under a polarizing optical microscope (POM). Some of derivatives checked by differential scanning calorimetry (DSC) technique was used to obtain thermograms of phase transition, enthalpy and entropy change. Characterization of some homologues was carried out by means of standard spectroscopic methods; infrared, proton magnetic resonance and ultraviolet spectroscopy. The prepared series were also compared with other structurally similar compounds to understand the effect of the relative position of groups and the effect of molecular length on thermal stability and mesophase length.