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In the reaction system with NaBH 4 as a hydrogen donor, inhibiting the formation of hydrogen is the key to promote the efficient catalytic hydrogenation of CO 2. In this study, nanoscale zero-valent nickel supported on carbon nanofibers (Ni0/CNFs) was fabricated as a catalyst for CO 2 hydrogenation in aqueous NaBH 4 solution. The characteristics of Ni0/CNFs were examined. By SEM, it was observed that spherical nickel nanoparticles were distributed homogeneously on the surface of strip-shaped carbon nanofibers. EDS mappings indicated that elements were evenly distributed on the catalyst, which might contribute to the uniform exposure of active sites. Via XRD, it was determined that all the diffraction peaks corresponded to the crystal face of nickel metal and that the absence of diffraction peaks of carbon nanofibers indicated that the crystallinity of the carrier was low. XPS study showed that nickel existed on the catalyst surface in two forms: zero valence metal and oxidation state. The effects of catalyst addition amount, NaBH 4 concentration, NaOH dosage, stirring rate on the yield of formate and hydrogen generation rate (HGR) were investigated. By optimizing the above parameters, the concentration of formate reached 150 mmol/L and the hydrogen production rate was 10.55 mL/min. Compared with the non-catalytic conditions, the concentration of formate increased by 57 % and the HGR decreased by 78 %. Moreover, the relationship between CO 2 hydrogenation and NaBH 4 hydrolysis was clarified. This research could enhance comprehension of CO 2 hydrogenation in aqueous NaBH 4 solution and contribute to the development of CO 2 capture and utilization storage technology. The significance of this study lies in clarifying the connection between CO 2 hydrogenation and borohydride hydrolysis in CO 2 catalytic hydrogenation technology. • Ni0/CNFs promoted CO 2 catalytic hydrogenation by inhibiting NaBH 4 hydrolysis. • The relationship between CO 2 hydrogenation and NaBH 4 hydrolysis was clarified. • Catalytic hydrogenation of CO 2 was performed under ambient conditions. [ABSTRACT FROM AUTHOR]