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Chemical looping reforming (CLR) technique is a prospective option for hydrogen production. Improving oxygen mobility and sintering resistance are still the main challenges of the development of high-performance oxygen carriers (OCs) in the CLR process. This paper explores the performance of Ni/CeO2 nanorod (NR) as an OC in CLR of ethanol. Various characterization methods such as N2 adsorption-desorption, X-ray diffraction (XRD), Raman spectra, transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), H2 temperature-programmed reduction (TPR), and H2 chemisorption were utilized to study the properties of fresh OCs. The characterization results show the Ni/CeO2-NR possesses high Ni dispersion, abundant oxygen vacancies, and strong metal-support interaction. The performance of prepared OCs was tested in a packed-bed reactor. H2 selectivity of 80% was achieved by Ni/CeO2-NR in 10-cycle stability test. The small particle size and abundant oxygen vacancies contributed to the water gas shift reaction, improving the catalytic activity. The covered interfacial Ni atoms closely anchored on the underlying surface oxygen vacancies on the (111) facets of CeO2-NR, enhancing the anti-sintering capability. Moreover, the strong oxygen mobility of CeO2-NR also effectively eliminated surface coke on the Ni particle surface.