The phase structures and electrochemical properties of the V TiNi Hf (x50-0.25) alloys were investigated. It is found that the 2.1 0.5 xaddition of Hf (x$0.05) into the V TiNi alloy changes the secondary phase from the b.c.c. TiNi-based phase to a C14 Laves phase 2.1 0.5with hexagonal structure, in the form of a three-dimensional network along the grain boundaries of the main phase. The amount of theC14 Laves phase increases with increasing Hf content. The discharge capacity of the Hf added alloys remains high. The V TiNi Hf 2.1 0.5 0.05alloy electrode has a discharge capacity of 444 mAh/g (discharge current: 25 mA/g), exceeding that of the V TiNi alloy. Proper Hf 2.1 0.5content (x#0.12) is advantageous for improving the high-rate dischargeability of V TiNi Hf alloys. The presence of Hf always leads 2.1 0.5 xto a degradation in cycle stability of the alloys, mainly due to the increase of the V content in the secondary phase and the increasingtendency to form cracks on the alloy surface in cycling.