Hydrazine borane N2H4BH3 (denoted HB) is a novel candidate in hydrogen generation by catalytic hydrolysis. The challenge with this material is the dehydrogenation of the N2H4 moiety, which occurs after the hydrolysis of the BH3 group. This challenge requires the utilization of a reactive and selective metal-based catalyst. In this work, we considered various transition metal salts as precursors of in situ forming catalysts by reduction in the presence of HB. According to their reactivity, the metals studied can be classified into 3 groups: (1) Fe- and Re-based catalysts, showing a limited reactivity in the hydrolysis of the BH3 group; (2) Co-, Ni-, Cu-, Pd-, Pt- and Au-based catalysts, only active in the hydrolysis of BH3 (3 mol H-2 per mol HB generated); (3) Ru-, Rh, and Ir-based catalysts, being also active in the decomposition of N2H4. With the Rh-based catalyst, characterized as agglomerated Rh-0 nanorods (10 x 4 nm) by XRD, TEM, SAED and XPS, 4.1 mol H-2 + N-2 per mol HB can be produced at 50 degrees C. Rhodium is thus a possible candidate for synthesizing nanosized particles and bimetallic nanoalloys in order to tune its reactivity and increase its selectivity up to the targeted conversion of 100%. Our main results are reported herein and the behavior of the metals is discussed. Copyright (C) 2012, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.