It is highly desirable to develop efficient and cost-effective composite catalysts to replace noble metal Pt for hydrogen evolution reaction (HER). For an excellent HER catalyst, both the adsorption and desorption of intermediate H atoms on it should be easy. However, except metal platinum, most individual species cannot satisfy this requirement. Fe-B is an active HER catalyst with strong ability to adsorb H atoms. In our previous work, we found that when Fe-B alloy was decorated with metal Fe particles (Fe-B@Fe), the resultant composite displayed a significant synergic effect for HER compared to single Fe-B and Fe. The role of the decorated Fe on Fe-B is to improve H-2 desorption. Because the desorption of H-2 molecule from Ni is easier than from Fe, we expect Fe-B@Ni to be a more efficient HER catalyst than Fe-B@Fe. Herein, we transform Fe-B@Fe into Fe-B@Ni by a facile displacement reaction. As a proof of concept, the as-prepared Fe-B@Ni catalyst exhibits much higher electrocatalytic and photocatalytic activity for hydrogen production than the pristine Fe-B@Fe. At the current density of -100 mA cm(-2), the overpotential of Fe-B@Ni in 1.0 mol L-1 KOH is close to that of 20 wt% Pt/C. The highest apparent quantum yield (AQY) for dye-sensitized photocatalytic hydrogen evolution reaches 51% at 420 nm. The possible mechanisms have been proposed. These findings provide new insights for designing and fabricating new HER composite catalysts for electrocatalytic and photocatalytic hydrogen evolution. (C) 2020 Elsevier Inc. All rights reserved.