This paper deals with improvement in the hydrogenation behavior of LaNi5 type alloys brought in through material tailoring by substitution of elements having higher electron attractive power and bigger sizes than that of Ni. Although substitutions by both Co and Fe were investigated, optimum results were obtained only through Fe. The higher electron attractive power of Fe, Co (3d(6), 3d(7) as against 3d(8) of Ni) is expected to lead to possibility of higher number of hydrogen atoms in the unit cell, thus resulting in higher storage capacity. Fe substitution has been found to be more affective in the enhancement of storage capacity. The size of the Fe atom (1.72 angstrom) is higher than that of Ni (1.67 angstrom) by about 6.13%. This may lead to larger size of interstitial voids. Thus, there may be higher number of interstitial voids occupied by hydrogen for the Fe substituted version as compared to Ni alone. Keeping these aspects in view, we have investigated Fe substituted version of LaNi5, i.e. the material La(Ni1-xFex)(5). It has been found that all the phases of La(Ni1-xFex)(5) exhibit better hydrogenation characteristics than the parent material LaNi5. Thus, the storage capacity of La(Ni1-xFex)(5) for x = 0, 0.05, 0.10, 0.20, 0.25, 0.30 are similar to 1.5, 1.93, 1.96, 2.20, 1.78 and 1.60wt%, respectively. The material La(Ni0.80Fe0.20)(5) has been found to exhibit the highest storage capacity similar to 2.20wt%. The possible reasons for the enhancement of storage capacity of Fe substituted LaNi5 have been described and discussed. (C) 2007 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved.