The measurements of the desorption pressure-composition-temperature (P-C-T) of the TixZr1−xNiyV2−y (0 ≤ x ≤ 1,0 ≤ y ≤ 2) alloy have been investigated by means of a 32 factorial design method. The response surface function of hydrogen desorption between 0.01 and 10 atm was calculated by Yates' algorithm. Alloy with x = 0.35, y = 0.60 (i.e., Ti0.35Zr0.65Ni0.6V1.4) was found to possess maximum hydrogen desorption capacity. When examined by EDAX and SEM, this alloy shows three distinguishable phases and exhibits C14 structure. The effect of substitution of Mn and Ni for V was also studied. Alloy such as Ti0.35Zr0.65Ni1.2V0.4Mn0.4 has nearly a pure C14 structure with 89% hydrogen desorption ability. This alloy has 255 mAh/g, 231 mAh/g, and 210 mAh/g capacities at 25 mA/g, 50 mA/g, and 100 mA/g discharge rates, respectively. This indicates that the substitution of Mn and Ni for V not only can improve its hydrogen desorption ability, but also make the alloy structure more uniform and more suitable to be an electrode material.