A series of copper(II) complexes 1 derived from unsymmetric 1,3,4-thiadiazoles 2 exhibiting mesogenic properties are reported. All the precursors 2 and 3 exhibited smectic A or/and smectic C phases, whereas, copper complexes formed nematic, SmA or SmC phases. The mesophases formed by derivatives 2 and 3 were probably attributed to the H-bondings induced both intramolecularly or/and intermolecularly between amide (-NH) and phenolic (-OH) groups. The crystal and molecular structures of mesogenic 2-(5-(2-(hexyloxy)naphthalene-6-yl)-1,3,4-oxadiazole-2-yl)phenol (2; n=6, m=6) were determined by means of X-ray structural analysis. It crystallizes in the monoclinic space group P-1, with a=7.4255(18) Å, b=8.209(2) Å, c=17.315(5) Å, and Z=2. An intermolecular H-bond (d=1.89 Å) between N2 and H1A atoms with an angle of 161.5° was observed. All molecules were packed as tilted layer arrangement and a π-π interaction (ca. 3.56 Å) was observed. Variable temperature FTIR and 1H NMR spectroscopies were also used to probe the possible H-bondings formed in compound 2 (m=0, n=6). The fluorescent properties of these compounds 2 were examined. All λmax peaks of the absorption and photoluminescence spectra occurred at ca. 359-363 nm and 519-537 nm, respectively. Excited state intramolecular proton transfer (ESIPT) reaction in this type of ortho-hydroxy-1,3,4-thiadiazole was also observed.