Identifying new uses for glycerol, a waste of biodiesel production from transesterification of vegetable oils, is of great current interest. Towards this end, catalytic oxidation of glycerol to produce the high-value chemical dihydroxyacetone (DHA) is a promising approach. The challenge, however, is the relatively complex reaction network. The kinetics of the complete glycerol oxidation network over Pt-Bi/C catalyst was investigated systematically in this study. Based on a detailed reaction mechanism including adsorption/desorption and reaction steps on the catalyst surface, a kinetic model was developed. To overcome the difficulty in finding the global optimum in the model, the full complex network was decomposed into five progressively larger sub-networks with different intermediates as initial reactants. The corresponding reactions starting with these initial reactants were conducted and the collected data were used to fit the kinetic model for each sub-network The experimental and calculated results were in good agreement and the kinetic parameters for each step were obtained. These results can be used to design and develop new appropriate catalysts with high stability, activity and selectivity for DHA. In fact, this approach is a powerful tool for the microkinetic study of other complex reaction networks as well. Based on the concentration of each component and rate expression of each reaction step, a simplified network was identified and studied. The parameters thus obtained can be used to develop reactor models which could be used to determine the optimum operating reaction conditions for maximizing the yield of desired product DHA. The effective conversion of glycerol to high value chemical will increase the profitability of biodiesel production, a promising renewable energy source. (C) 2011 Elsevier B.V. All rights reserved.