The effect of Ce substitution for Ti on the microstructure, hydrogen absorption characteristics and electrochemical properties of Ti0.85−xCexVFe0.15 (x = 0, 0.02 and 0.05) is studied in detail. In the Ti–V–Fe series, the composition Ti0.85VFe0.15 which crystallizes in single phase BCC structure shows the highest hydrogen storage capacity of 3.7 wt%. In the present study, the effect of Ce addition (2 and 5 at%) on the hydrogen absorption properties of Ti0.85VFe0.15 has been investigated by X-ray diffraction, electron probe microanalysis (EPMA) and pressure–composition isotherm studies. The hydrogen absorption capacity is found to be higher for the Ce substituted alloys. The alloys Ti_0.85VFe_0.15, Ti_0.83Ce_0.02VFe_0.15 and Ti_0.80Ce_0.05VFe_0.15 show maximum hydrogen storage capacities of 3.7, 4.02 and 3.92 wt%, respectively. Kinetic studies show that the hydrogen absorption is quite fast for all the three alloys and they reach near saturation value in about 120 s. Electrochemical studies of the Ce (2 at%) substituted alloy, Ti_0.83Ce_0.02VFe_0.15 show higher electrocatalytic activity for the hydrogen electrode reactions as compared to Ce-free parent compound, Ti_0.85VFe_0.15.