Developing robust, stable, low-cost, and highly active environmentally friendly electrocatalysts for the hydrogen evolution reaction (HER) is necessary for realizing alternative clean energy sources. We prepared highly stable ultrafine NiCo@borondoped carbon (NiCo@BC) by using a simple reduction method. As an excellent and highly stable HER electrocatalyst, the asprepared NiCo@BC 500°C nanoparticle catalyst displays a satisfying HER performance, delivering a low geometrical overpotential of 209 mV at 10 mA cm À 2 current density, a small Tafel slope of 60 mV dec À 1 , and an outstanding time-dependent stability after 200 hours in an alkaline solution, which is one of the best reported B-doped HER electrocatalysts. The outstanding catalytic activity arises from synergetic relationships between B-doped carbon and NiCo, coexisting in the asprepared hybrid product with the crystalline nature of the hybrid NiCo@BC products bearing plentiful catalytically active sites and good electrical conductivity. The promising combination of robust stability, high catalytic performance, and a simplistic preparation approach provides a new-type of electrocatalyst for clean energy technologies.