Different Ni-Se nanostructures are in situ prepared based on Ni foam (NF) through facile hydro(solvo)thermal selenization process under different solvents including ethanol, N, N-dimethylformamide (DMF) and water. The as-prepared Ni-Se/NF samples demonstrate different phase, composition and surface morphology through physical characterization. XRD and SEM indicate that Ni-Se growing in water demonstrates mixed crystal phases of NiSe and Ni3Se2 with nanorod-like nanostructures, whereas samples Ni-Se prepared in DMF and ethanol are pure NiSe phase with nanoneedle-like nanostructures. Electrocatalytic activity for hydrogen evolution reaction (HER) of all samples has been evaluated in alkaline solution. NiSe/NF (ethanol) demonstrates the smallest overpotential (170.5 mV) to reach j = −10 mA cm−2 for HER and excellent long-term stability. The enhancement of electrocatalytic activity in alkaline solution may be ascribed to its good conductivity and large electrochemically active surface area (ECSA).