Effects of of Mn and Ce addition on hydrogen-storage microstructure and properties of (Ti0.27Cr0.33V0.4)100-xMnxCey alloy have been investigated by XRD, SEM/EDS and P-C isotherm measurements. The results show that the addition of Mn enhances the precipitation of Ti-rich phases. With the increase of Mn addition, the lattice parameters of bcc main phase are reduced, the plateau pressure of alloys is increased, and the amount of residual hydrogen in alloys is decreased. The maximum capacity of effective hydrogen storage is obtained at 8at% of Mn content in alloys. Based on this alloy, the addition of Ce inhibits the precipitation of Ti-rich phases and facilitates homogeneous distribution of composition in the bulks. With the increase of Ce addition, the lattice parameters of alloys are increased, plateau pressure of alloys is improved, and the maximum capacity and effective capacity of hydrogen storage are raised.