The effects of composition and heat-treatment on the protium absorption–desorption properties of Ti–V–Cr alloys were investigated. It was found that the Ti–35V–40Cr alloy shows a 2.6 mass% protium capacity. The plateau pressure of the Ti–35V–xCr alloys increased with decreasing lattice constants associated with increasing Cr content. The main phase of the as-cast Ti–xV–Cr (Cr/Ti=40/25) alloys containing more than 15%V was a b.c.c. phase. These b.c.c. alloys exhibited a 2.4 mass% protium capacity. Heat-treatment over 1673 K was effective on stabilizing the b.c.c. structure for the Ti–xV–Cr (Cr/Ti=2/3) alloys with low V content. The Ti–5V–57.5Cr alloy heat-treated at 1673 K for 1 h yields a high capacity of 2.8 mass% protium, which is the highest value at 313 K reported so far. The alloy is economically promising since it contains low amounts of expensive V metal.