Hydrogenation properties of the vanadium-rich ternary V-Ti-Cr alloy was investigated, which is of interest as a hydrogen carrier for fuel-cell vehicles. The dependence of hydrogen content of the hydrides with low plateau pressure (β phase) on the unit cell volume of the dehydrogenated alloys (α phase) is found to be different from that of the hydrides (γ phase) with high plateau pressure. By optimizing the alloy composition, a large effective hydrogen storage capacity of 2.62 mass% is obtained.