We used melt polymerization method to prepare a series of aromatic liquid crystals (LCs) based on aromatic ester and amide units with the reactive methyl-maleimide end group. and then the resulting thermally cross-linked LCs to produce LC thermoset films by means of solution casting and the followed heat treatment. The synthesized LCs and LCTs were characterized by Fourier transform infrared (FTIR) spectroscopy, differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), thermo-mechanical analysis (TMA), X-ray diffractometry (XRD). and polarizing optical microscopy (POM) with a hot stage. All of the LCs prepared by melt polymerization method formed smectic mesophases. The thermal properties of the LC and LCT films were strongly affected by the mesogen units in the main chain structures. The thermal expansion coefficients of samples were in the range of 27.72 similar to 50.95 ppm/degrees C.