A series of Pt/CeO2 catalysts with varied sizes of Pt domains are prepared and evaluated in propane total oxidation reaction, to investigate the structural sensitivity regarding the particle sizes and metal‐support interactions. Over Pt single atoms, clusters or nanoparticles (NP), the obtained similar turnover frequencies and apparent activation energies suggest the reaction is structure insensitive to the sizes of Pt domains. Nonetheless, detailed kinetic study reveals different adsorption behavior of reactants (C3H8 and O2) over these Pt species. Following a Langmuir‐Hinshelwood mechanism, C3H8 and O2 competitively adsorb on Pt surface. The adsorption of C3H8 and O2 on Pt single atom is much easier than on Pt nanoparticles due to its lower coordination. These findings provide experimental evidences for the reaction behavior of C3H8 oxidation over Pt/CeO2 catalysts, and lay a foundation for further understanding of the structure‐property relationship.