Copolyesters are one of the most significant classes of polymers with repeating carboxylate group in their backbone. A novel random copolyester was synthesized using 1,4-dihydroxy naphthalene, quinol with phthaloyl chloride as dissimilar diols and diacid chloride monomers. The obtained polymers were characterized by ultraviolet-Visible spectroscopy (UV-Vis), Fourier transform spectroscopy (FTIR), nuclear magnetic resonance (NMR), thermogravimetric analysis, and differential scanning calorimeter. The surface morphology and crystalline nature of the polymers were analyzed using scanning electron microscope (SEM) and polarizing optical microscope. From the above, all details the synthesized polyesters are novel to possess the nature of liquid crystalline. Results of the exploration revealed that the innovative entries of copolymer were recommended into the set of liquid crystalline copolymers.