Mass transfer governs the overall catalytic performance of heterogeneous catalysts considerably; however, this fundamental research has often been ignored. Here, macroporous SiO2-supported Pt nanoparticle (Pt/SiO2-M) and mesoporous SiO2-supported Pt nanoparticle (Pt/SiO2-m) catalysts were specifically fabricated by a facile thermal reduction step to engineer the resultant Pt nanoparticles showing similar physiochemical properties while possessing completely different porous microstructures exclusively originating from SiO2 supports. On this basis, a platform to explore the crucial mass transfer difference affecting catalytic activity is then established by systematically practicing industry-important benzene oxidation measurements. State-of-the-art characterization techniques confirmed that all of the as-synthesized Pt/SiO2 catalysts indeed exhibited almost identical Pt sites, excluding catalytic discrepancies raised from Pt nanoparticles. Importantly, Pt/SiO2-M displayed complete benzene oxidation capabilities at a lower temperature than that for Pt/SiO2-m, accrediting to the macroporosity-induced faster desorption rate of H2O and CO2, thus making it capable of enhancing the high utilization of Pt sites. This work highlights the importance of improving mass transfer capability toward supported nanoparticulate catalysts, demonstrating the significance of designing novel macroporous supports for industry-important catalysis implications.