Multiwall carbon nanotubes (MWCNTs) supported PtSb alloy nanoparticles were prepared and used in the selective oxidation of glycerol to dihydroxyacetone (DIHA) in a base-free aqueous solution. The structure and morphology of the prepared PtSb/MWCNTs catalyst were characterized and compared with that of Pt-Bi/MWCNTs. It was found that Sb homogenously entered into the lattice of Pt and PtSb alloy nanoparticles formed in PtSb/MWCNTs, but Pt particles in Pt-Bi/MWCNTs were wrapped by a layer of Bi2O2CO3. PtSb/MWCNTs is extremely active for the selective oxidation of glycerol to DIHA. The turnover frequency of surface Pt atoms in PtSb/MWCNTs increased from 341.5 (of Pt/MWCNTs) to 878.1 h(-1). At the same time. DIHA is relatively 'stable' over the homogenous PtSb alloy nanoparticles, which also depressed the cleavage of C-C. (C) 2012 Elsevier B.V. All rights reserved.