The perovskite catalysts La0.75Sr0.25Cr0.5X0.5O3±δ (where X= Mn, Fe and Co) were prepared by combustion synthesis and the influence of transition metals B-site substitution on the structural and catalytic properties of the catalysts in steam reforming of both pure and by-product glycerol to produce hydrogen-rich gases for utilization in solid oxide fuel cell was investigated. All the catalyst systems were found very active and selective with the Fe-substituted catalyst slightly more active. Hydrogen yield and coke suppression was better in the Mn-substituted catalyst which was also structurally more stable in fuel environment. Impregnation of Ni into the lattice structure of the pre-reacted both A-site and B-site stoichiometric catalysts from nickel nitrate solution and subsequent redox exsolution of Ni nano particles supported on the oxide surface of the materials has significantly improved the hydrogen yield by enhancing water-gas-shift reaction (WGSR). Thus, extent of the exsolution phenomenon observed in the materials followed the order LSCM > LSCC > LSCF.