A series of Fe-substituting cobalt C14-predoninating AB 2 alloys with the general formula Ti 12 Zr 21.5 V 10 Cr 7.5 Mn 8.1 Fe x Co 8−x Ni 32.2 Sn 0.3 Al 0.4 (x=0–5) were studied for the impacts of Fe to structure, gaseous, and electrochemical hydrogen storage properties. All alloys exhibit hyper-stoichiometric C14 main phase due to the formation of A-rich non-Laves secondary phases and the loss of Zr and Ti in the melt. Lattice parameters together with the unit cell volume increases and then decreases with increasing Fe-content which indicates the existence of anti-site defects. The amount of TiNi secondary phase increases with the increase of Fe-content up to 4% and shows a detrimental effect to the high-rate dischargeability of the alloys. Most of the gaseous storage characteristics remain unchanged with the addition of Fe. In the electrochemical properties, Fe-addition in the AB 2 alloys facilitates activation, increases the total electrochemical capacity and effective surface reaction area, decreases the half-cell high-rate dischargeability and bulk hydrogen diffusion, and deteriorates both −10 and −40°C low-temperature performance. Fe-substituting Co in AB 2 alloys as negative electrode of nickel metal hydride battery can reduce the raw material cost with the trade-off being mainly in the low-temperature performance.