In this study, nickel-cobalt@functionalized multi-walled carbon nanoparticles (NiCo@f-MWCNT NPs) were synthesized, analysed, and used for hydrogen generation via methanolysis on NaBH4. For the NPs synthesis, two steps were conducted (i.e., i: MWCNT was functionalized in an acid medium to support NPs (f-MWCNT); ii: NiCo NPs were synthesized and supplemented with f-MWCNT). Various characterization techniques were used to examine the morphological structure of NiCo@f-MWCNT NPs. The transmission electron microscope (TEM) results showed that the NPs were sized as 3.941 ± 1.094 nm with a spherical structure. The X-ray diffraction analysis (XRD) results indicated an average crystalline size of 1.46 nm. The evaluation of the catalytic performance for hydrogen production revealed that the turnover frequency (TOF) was calculated to be 2934.4 min− 1 with activation energy (Ea) and enthalpy (∆H) of 39.29 kJ/mol and 36.74 kJ/mol, respectively, which indicates high viability for hydrogen transport and generation application and processes. [ABSTRACT FROM AUTHOR]