A hollow nanoflower material CuCo2O4@NFs with abundant oxygen vacancies (VO) and cobalt vacancies (VCo) was prepared by a simple method. The novel material CuCo2O4@NFs showed excellent oxidation activity, cleaving the β-O-4 bond in lignin model compounds. Conversion of the substrate was as high as 99.02%, and the yield of the main product, phenol, reached 49.50%. Structural analysis showed that the petal and cavity form of the material increased its specific surface area, which facilitated its full contact with O2 molecules. Moreover, the VO generated by lattice oxygen detachment during annealing favor the adsorption of O2, and the VCo generated through lattice distortion induced by Cu-metal doping promoted the detachment of oxygen intermediates. The synergy of these two defects improved the rate of the rate-limiting step. Density functional theory calculations revealed that the synergistic effect of VO and VCo narrowed the gap between the Fermi energy levels and the d-band center, thereby enhancing electron mobility. Finally, excellent recyclability of CuCo2O4@NFs was confirmed through cycling experiments. The application of this material provided technical support for the efficient cracking of lignin into high-value-added chemicals and realized the effective utilization of woody biomass resources.