Renewable alternative energy sources are required to decrease or eliminate the use of environmentally unfriendly fossil fuels. Hydrogen produced by electrolysis has been identified as one such renewable energy carrier. In the current work, Ni nanoparticle (NP)-decorated multiwall carbon nanotube (MWCNT) electrocatalyst cathodes are prepared by a simple two-step procedure. MWCNTs are grown on stainless steel meshes by thermal-chemical vapour deposition (t-CVD) and then decorated with Ni NPs by pulsed laser ablation (PLA). The morphological and electrochemical properties of the produced Ni NP/MWCNT cathodes were characterized through electron microscopy and linear Tafel polarization (LTP)/electrochemical impedance spectroscopy (EIS), respectively. SEM and TEM imaging revealed that the Ni NPs deposited by PLA are on the order of 4 nm in diameter with a narrow size distribution. The LTP measurements showed that the electrocatalytic activity of the Ni NP/MWCNT cathodes towards the hydrogen evolution reaction (HER) is dependent on PLA time and shows a maximum at t(PLA) = 40 min. EIS measurements revealed that the HER response is characterized by a two time constants process representing HER kinetics and adsorption of hydrogen. (C) 2014 Elsevier B.V. All rights reserved.