A new series of mesogenic unsymmetrical azines, N-[4-(alkoxy)-2-hydroxybenzylidene]-N'-(4-n-alkoxybenzylidene) azines, ROC6H4CH=N-N=CHC6H3OHOR, where R = CmH2m+1 (m = 6, 8, 10, 12, and 14), and their copper (II) complexes has been synthesized. They were characterized by elemental analyses, Fourier transform infrared (FT-IR), H-1 and C-13 nuclear magnetic resonance (NMR) spectra, ultraviolet (UV)-visible, and magnetic susceptibility measurements. The copper (II) complexes are square planar. The mesomorphic properties of these compounds were investigated by differential scanning calorimetry and polarizing microscopy. The unsymmetrical azines with m = 6, 12, and 14 exhibit monotropic nematic, enantiotropic, and monotropic smectic A phases, whereas azines with m = 8 display enantiotropic nematic and m = 10 display both enantiotropic smectic A and nematic mesophases in the heating and cooling cycles. The copper (II) complexes of the azines are nonmesomorphic in nature with high clearing temperatures and displayed polymorphism (crystal-crystal transitions) in both the heating and cooling cycles.