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An alternative reduction route of Pd-promoted Co 3 O 4 supported on SBA-15 under ethanol dehydrogenation and decomposition (ED) was studied by an operando time-resolved X-ray absorption spectroscopy (TR-XAS) to understand the insight nature of materials. The catalysts, xPd-10Co/SBA-15, were prepared by co-impregnation method where the Pd content, x = 0.2, 0.5 or 1.0 wt% and Co content = 10.0 wt%. The precursors were transformed to PdO and Co 3 O 4 after calcination and to metallic form after reduction. The reducibility of Co 3 O 4 to metallic Co in 1Pd-10Co/SBA-15 was 98.0%, whereas the metallic form was not produced in the absence of Pd. This catalyst also provided the highest H 2 yield of 80% from ED at 500 °C. The ED-reduced 1Pd-10Co/SBA-15 was tested in reverse water gas shift reaction (RWGS) and characterized by the operando TR-XAS. The CO selectivity from CO 2 was 97.8%, slightly higher than conventional H 2 -reduced 1Pd-10Co/SBA-15. [Display omitted] • Reduction of Co 3 O 4 in ethanol dehydrogenation and decomposition (ED) was disclosed. • Effect of Pd loading on the reducibility of Co 3 O 4 to metallic Co in ED was studied. • Pd with 1.0 wt% provided the highest reducibility of Co 3 O 4 and H 2 yield under ED. • Pd-Co/SBA-15 reduced under ED was active in reverse water gas shift (RWGS). • Pd-Co/SBA-15 reduced under ED provided 97.8% CO selectivity from RWGS. [ABSTRACT FROM AUTHOR]