For Ni-MH batteries, crystalline Mg-based alloys such as MgNi, Mg2Ni, REMg12, and La2Mg17 are regarded as hopeful negative electrode materials. Even though these alloys are inexpensive and have promising discharge capacity, they hardly ever electrochemically absorb or desorb hydrogen at room temperature. In this paper, the MgNi-based Mg50-xTixNi45Al3Co2 (x = 0, 1, 2, 3, 4) alloy electrodes were fabricated. The surface of the as-cast alloys was modified by mechanical Ni coating. The nanocrystalline and amorphous Mg50-xTixNi45Al3Co2 (x = 0, 1, 2, 3, 4) + 50 wt%Ni alloys for Ni-MH batteries were prepared using mechanical ball milling. The effects of Ti content and ball milling time on the structure and electrochemical hydrogen storage properties of the alloys were investigated. The electrochemical testing reveals that the as-milled alloys can electrochemically absorb and desorb hydrogen well at room temperature. Without any activation, the milled alloys can achieve maximum discharge capacity in the first cycle. With the extension of ball milling time and the increase of Ti content, the cycle stability and discharge capacity of the alloys are significantly enhanced. The electrochemical impedance spectrum, high rate discharge ability, potentiodynamic polarization curve, and potential-step measurement all indicate that the electrochemical kinetics of the prepared alloys initially increase and subsequently decrease with the increase of Ti content, while significantly improve with the prolongation of milling time.