Developing noble metal-free multifunctional electrocatalysts to catalyze water oxidation is vital for future renewable energy systems. Herein, through several defect modifications, the CeC2-TiO2 nanocomposite on the strength of enriched oxygen vacancies was successfully fabricated by facile hydrothermal method on SS (stainless steel) substrate, attributed to the conductive ability for fast electron transportation. A well-defined phase growth, vibrational bonding of metal atoms, morphological determination, and elemental composition for synthesized heterostructured electrocatalysts were revealed by XRD, FTIR, TEM, and EDX, respectively. XPS has complied to understand the moderate binding energies of CeC2-TiO2 for OER intermediates, which signifies the strong interactions between electronic states of Ce, C, Ti, and O atoms. With the plentiful catalytic active sites, the resultant CeC2-TiO2 entails low overpotentials of only 169 mV and 108.8 mV/dec Tafel slope to afford 10 mA cm−2 for OER in 1.0 M KOH are tested through cyclic and linear sweep voltammogram measurements, thereby exhibit promising activity in alkaline water electrolysis. EIS measurements revealed a decreased polarization resistance for the composite dominated by the small semicircle diameter, corresponding to the adsorption of intermediates. Finally, observed results strongly recommended that the CeC2-TiO2 catalyst exhibited superior OER performance due to excellent electrical chemical coupling between CeC2 and TiO2.