The microstructure of V-Ti-Ni alloy affects not only the hydrogen separation performance, but also the mechanical properties and formability. The microstructure, hardness and tensile properties of multiphase V100-2x-Tix-Nix (X=10, 15, 20) alloys for hydrogen separation were investigated. The microstructure of V100-2x-Tix-Nix alloys ingot consists of dendritic phase (V base solid solution) and interdendritic phase (NiTi and NiTi2). With the increase of the content of Ti and Ni in the alloy, the volume ratio of interdendritic phase in the alloy increases, and blocks the connection of dendrite arm due to forming a continuous network. At room temperature, the bulk hardness, tensile strength, elongation and reduction of area of the alloy increase with the increase of Ti and Ni content. V based solid solution and NiTi2 phase are the main factors affecting the bulk hardness of the three alloys. The three alloys are brittle materials at room temperature. The content of NiTi in the alloy has a great influence on the elongation of the alloy.