The present study deals with investigations on synthesis, characterization and hydrogenation behavior of the MmNi(5)-type hydrogen storage alloys Mm(0.9)Ca(0.1)Ni(4.9-x)Fe(x)Al(0.1) (x = 0, 0.1, 0.2 and 0.3). All the alloys are synthesized by radio frequency induction melting following the composite pellet route. The X-ray diffraction pattern of dehydrogenated alloy without iron, detects peaks corresponding to calcium hydride, which are absent in the XRD pattern of the alloy with iron. The hydrogenation behavior is monitored by means of activation curves, absorption-desorption pressure-composition isotherms, hysteresis factors and desorption kinetic curves. The substitution of Iron at the place of nickel in the alloys Mm(0.9)Ca(0.1)Ni(4.6-x)Fe(x)Al(0.1) (x = 0, 0.1, 0.2 and 0.3) gives an increase in the hydrogen storage capacity as 1.82, 1.90, 2.2 and 1.95 wt% corresponding to x = 0, 0.1, 0.2 and 0.3 respectively. The correlation between structural characteristics and hydrogenation behavior is described and discussed. opyright (C) 2011, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.