Carbon-supported Ni@Ag core-shell nanoparticles were synthesized and used as the anode electrocatalyst for direct borohydride-hydrogen peroxide fuel cell (DBHFC). The morphology, structure, and composition of the asprepared electrocatalysts are characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD), and energy dispersive spectroscopy (EDS). Electrochemical characterizations are performed by cyclic voltammetry (CV), chronoamperometry (CA), linear scan voltammetry with rotating disk electrode (LSV RDE), and fuel cell test. The catalytic behaviors and main kinetic parameters (e.g., Tafel slope, number of electrons exchanged, exchange current density, and apparent activation energy) toward BH 4 -oxidation on Ag/C and Ni@Ag/C electrocatalysts are determined. Results show that the as-prepared nanoparticles have a core-shell structure with the average size approximately 13 nm. The kinetics of NaBH 4 oxidation is faster for Ni@Ag/C than that for Ag/C. Among the as-prepared catalysts, the highest transition electron value and the lowest apparent activation energy are obtained on Ni 1 @Ag 1 /C; the values are 4.8 and 20.23 kJ mol −1 , respectively. The DBHFC using Ni 1 @Ag 1 /C as anode electrocatalyst and Pt mesh (1 cm 2 ) as cathode electrode obtains the maximum anodic power density as high as 8.54 mW cm − 2 at a discharge current density of 8.42 mA cm −2 at 25°C.