Structures and electrochemical properties of TiMn2-5x(V4Fe)x(x＝0.30，0.35)alloys were investigated. The results of XRD analysis show that the alloys are mainly composed of body centered cubic (bcc) phase, whose lattice parameters are enhanced with the increase of V and Fe content. The SEM images of the alloys show that there are some colonies in the matrix phase. The proportion of colony to the matrix decreases with increasing of V and Fe content. The electrochemical measurements show that TiMn0.25(V4Fe)0.35 alloy has unfavorable activation performance until temperature reaches 327 K, while TiMn0.50(V4Fe)0.30 alloy shows better activation performance, but passivation phenomenon was found in the process of charging at low temperature, which can be eliminated by heating to high temperature. The PCT curves of alloys show that the TiMn0.50(V4Fe)0..30 alloy has a good comprehensive performance, with a favorable plateau pressure at room temperature and wide plateau. The enthalpy and entropy in hydrogen desorption of TiMn0.50(V4Fe)0..30 alloy were also calculated and they are –36.1 kJ/mol, –126.9 J/(mol·K), respectively