Nanostructured Bismuth-based materials are promising electrodes for highly efficient electrochemical reduction processes such as hydrogen evolution reaction (HER). In this work, a novel sort of nanocomposite made up of partially reduced Bi2O3 into metallic Bi anchored on a 3D network of Ni-foam as a high-performance catalyst for electrochemical hydrogen reduction. The application of the hybrid material for HER is shown. The high catalytic activity of the fabricated electrocatalyst arises from the co-operative effect of Bi/Bi2O3 and Ni-foam which provides a highly effective surface area combined with the highly porous structure of Ni-foam for efficient charge and mass transport. The advantages of the electrode for the electrochemical reduction processes such as high current density, low overpotential, and high stability of the electrode are revealed. An overall comparison of our as-prepared electrocatalyst with recently reported works on related work is done.