Defect engineering holds significant promise for addressing the low conductivity and limited adsorption of reactant molecules in hydrogen generation catalysts. Herein, theoretical predictions based on the d-band center and electron localization function (ELF) calculations indicate that the introduction of Ce induces charge rearrangement, enhancing charge enrichment on Pt atoms. Inspired by these theoretical predictions, a series of PtCeOx/CoNi-LDH catalysts were fabricated for efficient hydrogen generation. The experimental results indicate that introducing metal defects will induce lattice expansion in CeOx doping, leading to the elongation of Pt–O bonds, which effectively reduces the bond energy of Pt–O bonds. The reduction in Pt–O bond energy facilitates the capture and adsorption of reactant molecules, thus exhibiting outstanding catalytic activity with a NaBH4 hydrogen generation rate (HGR) of 8992 mL min–1 gcat.–1. Density functional theory (DFT) calculations show that the adsorption-free energy of the rate-determining step in the PtCeOx/CoNi-LDH catalyst is ca. –3.59 eV, which is lower than the reaction barrier of PtOx/CoNi-LDH (–3.25 eV). This indicates that the PtCeOx/CoNi-LDH catalyst more effectively facilitates the formation of transition state intermediates. Guided by DFT predictions, the successful fabrication of high-efficiency PtCeOx/CoNi-LDH catalysts establishes a strong foundation for the design and development of future hydrogen generation catalysts.