Catalyst nanoparticles were synthesized using a novel “Cellulose Assisted Combustion Synthesis” technique. In this technique, an aqueous solution of metal nitrate and a reducing agent is impregnated on a thin cellulose paper. The paper is dried and locally ignited at one end to start combustion reaction that is self-sustained under optimum loading of reactive solution, continuously producing nanoparticles. The thin film helps in generating a quenching effect and limits nanoparticles sintering in post-combustion stages. This paper describes the synthesis of Cu, Ni and Co based nanomaterials that are found to be active for sustainable hydrogen production from bioethanol, that can further be produced from agricultural biomass. A detailed mechanistic study of nanoparticle evolution during synthesis process was conducted along with the reaction pathway analysis for hydrogen production from bioethanol. In-situ FTIR (DRIFTS) studies on the metal surfaces reveal the differences in their catalytic performance and help in explaining the observed product distribution.