Structures of Pt species derived from Pt-4(mu-CH3COO)(8) on an alpha-Al2O3(0001) single-crystal surface were studied by means of in-situ polarization-dependent total reflection fluorescence XAFS (EXAFS and XANES) techniques. The Pt-4 cluster framework was destroyed upon the deposition of Pt-4(mu-CH3COO)(8) by the reaction on the alpha-Al2O3 surface at room temperature. The isolated Pt species were converted to one-atomic layer thick Pt rafts with the Pt-Pt distance of 0.273 nm when the cluster was treated with H-2 at 373 K. The raftlike Pt clusters were stabilized by the formation of direct Pt-O-Al bonding with the alpha-Al2O3 surface. The raftlike Pt clusters were redispersed to isolated oxidized Pt species by the reaction with NO. They were also transferred to three-dimensional Pt particles by reduction with H-2 at 773 K.