Homologous series of double hydrogen bonded liquid crystals are designed, synthesized, and characterized. Double hydrogen bond is formed between glutaric acid (GA) and p-n-alkyloxy benzoic acids (nBAO, where n varied from pentyl to dodecyl), resulting in new complexes referred as GA+nBAO. Formation of hydrogen bond is conformed by the Fourier transform infra red spectroscopy. The synthesized mesogens are characterized by polarizing optical microscopy, differential scanning calorimetric studies, ensuing phase diagram from the obtained data. The isolated mesogens are found to exhibit orthogonal and tilted phases, namely, nematic, smectic C, smectic F, and smectic G. In addition to these characteristic phases, a new smectic ordering labeled as smectic X has been identified and characterized. Dielectric studies are performed to confirm the newly formed smectic X phase. Thermal equilibrium and odd even effect are evinced from the individual enthalpy values of the homologues. The magnitudes of experimental optical tilt angle in smectic C of all the homologues is fitted to a power law, and the value of exponent is found to concur with the mean field theory predicted value.