In this work, multiwalled carbon nanotubes (MWCNTs) promoted Co-B catalysts for NaBH4 hydrolysis have been designed and synthesized. The structural features of as-prepared catalysts have been investigated and discussed as a function of MWCNTs contents by Xray diffraction, X-ray photoelectron spectra, N-2 adsorption/desorption isotherms, scanning electron microscope. The results show that the catalysts still maintain an amorphous structure with the addition of carbon nanotubes promoter. However, the appropriate amount of MWCNTs promoter in Co-B catalysts leads to large specific surface area, fine dispersion of active components, increased active sites and high electron density at active sites. Moreover, hydrogen spillover on the catalyst is promoted, which contributes to regeneration of active sites and accelerating catalytic cycle. Among all the experimental samples, it is found that the Co-B catalyst promoted by 10 wt% carbon nanotubes exhibits optimal catalytic activity with remarkably high hydrogen generation rate of 12.00 L min(-1).g(catalyst)(-1)and relatively good stability. (C) 2019 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.