As a hydrogen storage alloy, the body-centered cubic (BCC) structure has been well studied due to its large hydrogen storage capacity. On this basis, the introduction of catalytic elements and an appropriate amount of C14 Laves phase can further improve the comprehensive hydrogen storage properties of hydrogen storage alloys. Based on this theory, (Ti32.5V27.5Zr7.5Nb32.5) 1-xNix (x = 0.03, 0.06, 0.09) high entropy hydrogen storage alloys with an appropriate amount of catalytic element Ni are prepared in this study. The raise in Ni content is accompanied by grain refinement of the dendritic structure, an increase in the number of grains and grain boundaries, and a gradual increase in the proportion of C14 Laves phase. The introduction of catalytic element Ni reduces the dissociation energy of hydrogen molecules. The increasing grain and grain boundaries increase more hydrogen absorption sites with lower activation energy. The diffusion channel provided by the appropriate amount of C14 Laves phase makes it easier for hydrogen atoms to diffuse into the main phase BCC phase with strong hydrogen absorption capacity, and the hydrogen atoms are trapped by vacancy defects with large hydrogen binding energy. The synergistic effect of the three factors ensures the improvement of hydrogen absorption performance of high entropy hydrogen storage alloys. (Ti32.5V27.5Zr7.5Nb32.5) 0.94Ni0.09 high entropy hydrogen storage alloy achieves excellent saturated hydrogen storage capacity of 2.78 wt % and 2.99 wt % at room temperature and 150 °C under 3 MPa hydrogen pressure, respectively. In addition, the introduction of Ni element reduces the thermal stability of metal hydrides, thereby improving the dehydrogenation performance of high entropy hydrogen storage alloys. The reversible phase transition occurs during the whole hydrogen absorption and desorption cycle.