Four different plant biomass, bamboo, cotton, soft wood and hard wood, were utilized as carbon precursors to fabricate porous carbon catalyst supports via a chemical free approach. Large surface area with unique mesoporous structure was successfully created in the carbon, which made them suitable for catalyst support. After decorating silver nanoparticles onto these carbon supports, nitroaromatics reduction reactions were performed to evaluate the catalyst activity. Results indicate that chemical composition and surface groups of carbon supports determine the metal catalyst nucleation/growth while the porous microstructure of support affects the mass transport of reactant/product across the liquid/catalyst interface. Among the four selected biomass, porous carbon manufactured from soft wood acquires the highest average pore size, pore volume, mesopore volume fraction and best catalytic activity after decorating silver nanoparticles. This work not only presents an environmental benign process that converts natural biomass into effective porous carbon catalyst supports, but also offers a comprehensive understanding of biomass structure/composition relating to their suitability as catalyst support.