In this article, we report synthesis and characterization of a novel homologous series of butyl 4-(4-(alkoxy)-2-hydroxybenzylideneamino)benzoates, CnLH (n = 6, 8, 10, 12, 14, 16) and their copper(II) complexes. The mesomorphic properties of these compounds were investigated by differential scanning calorimetry (DSC), polarizing optical microscopy (POM) and powder X-ray diffraction (XRD) studies. The ligands and their copper(II) complexes exhibit wide range of enantiotropic smectic A mesophase as confirmed by their typical optical texture under polarizing microscope. Thermal stability of the compounds is determined by thermo gravimetric analyses. DFT calculations have been performed using GAUSSIAN-09 program at B3LYP level to obtain the stable electronic structure of the ligand and its copper(II) complex.