The microstructures and electrode properties of Cr or Co-doped V2. 1 TiNi0. 5 Hf0. 05 M0. 113 (M= Cr, Co)hydrogen storage alloys were investigated. It is found that all alloys consist of a main phase of V-based solid solution with b. c. c. structure and a secondary phase of C14-type Laves phase with a three-dimensional network structure.After the doping of Cr or Co into V2.1 TiNi0. 5 Hf0.05, the abundance and unit cell volume of the main phase decrease,and those of the secondary phase increase. The electrochemical measurements show that the discharge capacities of Cr-doped V2. 1 TiNi0. 5 Hf0. 05 Cr0. 113 alloy and Co-doped V2.1 TiNi0. 5 Hf0.05 Co0. 113 alloy are less than that of V2. 1 TiNi0.5 -Hf0. 05 alloy, but their cycle stability and high-rate dischargeability are improved markedly. The results show that Cr or Co doping into V2.1 TiNi0. 5 Hf0. 05 alloy is significantly beneficial for the cycling stability.