XRD, SEM+EDS and electrochemical tester at 323K were adopted to measure phase structure and electrochemical properties of Ti1.8(VFe)CrNi0.2+x.wt%LaNi5 hydrogen storage composite. It has showed that main phase, which is BCC structure with alloy’s cellular crystal and Cr-Ni-Ti-Fe with BCT structure, transformed into Ti-V-Cr-Fe-Ni which is main phase of BCC structure with dentrite crystal. Electrochemical properties show that activity and discharge capacity and so on is changed regularly. When x is 5, activity and discharge capacity of the composite alloy is the best of all, which is active by 9 cycle time and the discharge capacity reach 360mAh/g. It can be certain that the formation of rod-like crystal and synergistic reaction between the second phase Cr-Ni-Ti-Fe phase and the main phase of BCC structure plays the most important role in ipproving the alloy’s electrochemical properties.