Vanadium is highly permeable to hydrogen which makes it one of the leading alternatives to Pd alloys for hydrogen-selective alloy membrane applications, but it is prone to brittle failure through excessive hydrogen absorption and transitions between the BCC α and BCT β phases. V–Ti–Ni alloys are a prospective class of alloy for hydrogen-selective membrane applications, comprising a highly-permeable vanadium solid solution and several interdendritic Ni–Ti compounds. These Ni–Ti compounds are thought to stabilise the alloy against brittle failure. This hypothesis was investigated through a systematic study of V70Ti15Ni15 by hydrogen absorption and X-ray diffraction under conditions relevant to membrane operation. Dissolved hydrogen concentration in the bulk alloy and component phases, phase identification, thermal and hydrogen-induced expansion, phase quantification and hydride phase transitions under a range of pressures and temperatures have been determined. The vanadium phase passes through three different phase fields (BCC, BCC + BCT, BCT + BCT) during cooling under H2 from 400 to 30 °C. Dissolution of Ni and Ti into the vanadium phase increases the critical temperature for β-hydride formation from <200 to >400 °C. Furthermore, the Ni–Ti phases also exhibit several phase transitions meaning their ability to stabilise the alloy is questionable. We conclude that this alloy is significantly inferior to V with respect to its stability when used as a hydrogen-selective membrane, but the hydride phase transitions suggest potential application for high-temperature hydrogen and thermal energy storage.