In this paper, we report the effect of adding Zr + V or Zr + V + Mn to TiFe alloy on microstructure and hydrogen storage properties. The addition of only V was not enough to produce a minimum amount of secondary phase and, therefore, the first hydrogenation at room temperature under a hydrogen pressure of 20 bars was impossible. When 2 wt.% Zr + 2 wt.% V or 2 wt.% Zr + 2 wt.% V + 2 wt.% Mn is added to TiFe, the alloy shows a finely distributed Ti₂Fe-like secondary phase. These alloys presented a fast first hydrogenation and a high capacity. The rate-limiting step was found to be 3D growth, diffusion controlled with decreasing interface velocity. This is consistent with the hypothesis that the fast reaction is likely to be the presence of Ti₂Fe-like secondary phases that act as a gateway for hydrogen.