A series of bithiophene-based compounds, 2-(5 '-alkyl-2,2 '-bithiophene-5-yl)-benzoxazole derivatives (nTBx), bearing different substituents (H, CH3, Cl, NO2) at the 5-position, were prepared and characterized. They exhibit enantiotropic mesophases with temperature ranges of 3 degrees C-61 degrees C and 4 degrees C-71 degrees C during heating and cooling, and nTBx with electron-withdrawing substituents (NO2, Cl) display higher clearing temperatures and wider mesophase ranges than those of corresponding homologues with electron donating substituents. Compared to biphenyl-based analogs (nB-x), nTBx show much larger red-shifted absorption bands (374-388nm) and photoluminescence emission peaks (453-458nm), thereby illustrating the impact of the bithiophene core on electronic properties originating from the pi-molecular orbitals.