Herein, we report a robust approach for the selective covalent functionalization of graphene oxide (GO) with 4-hydroxybenzoic acid (HBA) for developing polymeric nanocomposites based on liquid crystalline polymers (LCPs). The functionalization of GO with HBA was confirmed by Raman spectroscopy, Fourier transform infrared (FT-IR) spectroscopy, and X-ray diffraction (XRD) spectroscopy. The surface morphology of GO and functionalized GO (FGO) was studied using field emission scanning electron microscopy (FE-SEM). Furthermore, the interactions between FGO and LCPs have been investigated by FT-IR spectroscopy, whereas dispersion of GO and FGO in the LCP matrix was analyzed by FE-SEM. The better dispersion of FGO can be attributed to the hydrogen bonding and π-π stacking interactions between FGO and LCPs. Our results showed that even the addition of 5 wt% FGO in the LCP matrix significantly enhances the tensile strength and storage modulus of the pristine LCPs by 84% and 78% respectively. Compared to neat LCPs, FGO incorporated composites also demonstrate an improvement in the melting temperature (Tm) by 11 °C and glass transition temperature (Tg) by 12 °C. Furthermore, thermogravimetric analysis (TGA) was performed to evaluate the thermal stability of the composite. The 5 and 50% decomposition temperature for the LCP/FGO nanocomposites (containing 5 wt% FGO) increased by 75 °C and 107 °C respectively.