N-heteroaromatics as one of cornerstones in chemical processes are in the limelight, so the synthesis of N-heteroaromatics have been attracted a great deal of attention. Among the elegant methods for the preparation of N-heteroaromatics, the direct oxidative dehydrogenation of saturated compounds affording N-heteroaromatics is a simple and efficient tactic. In this work, CoOX-CeO2 composites synthesized by the pyrolysis of Co/Ce-BTC MOFs as the precursor were employed as a heterogeneous catalyst for the dehydrogenation of N-heterocycles under aerobic conditions. CoOX-CeO2 composites were analyzed by diversified characterization techniques of SEM, TEM, BET, XRD, XPS, and ICP-OES. The characterization results demonstrate that abundant oxygen vacancies on the surface and the synergistic effect of CoOX-CeO2 composites remarkably enhance the catalytic performance of CoOX-CeO2 catalysts. Furthermore, the catalytic performance of CoOX-CeO2 composites remained excellent after six recycles. This catalytic system provides an alternative tool for the effective synthesis of aromatic compounds.