A new kind of liquid crystalline material with an azo group in the molecular core was synthesized successfully. The chemical structures of the compounds were confirmed by mass spectrometry and 1H NMR. Their phase structures and transitions were investigated by differential scanning calorimetry. And the liquid crystalline behaviors were researched with polarized light microscopy experiments. The experimental results suggested that the compounds with a azo group in the molecular core can develop into a well-defined nematic phase.