Glycerol (propane-1,2,3-triol) has been an object of interest in recent years as a byproduct in the production of biodiesel, a parental molecule for syngas production, and a representative compound of the tar components derived from the carbohydrate fraction of biomass. Kinetic models describing the thermal degradation of glycerol toward lighter hydrocarbons and noncondensable gases are considered beneficial to an effective implementation of processes for its valorization. The aim of this work is to analyze and discuss the primary propagation reactions of glycerol, together with the ones of acetol (1-hydroxypropan-2-one) and 3-hydroxypropanal (the primary products of glycerol). This kinetic model is then evaluated in comparison with three independent sets of experimental measurements. The first one refers to pyrolysis experiments at intermediate temperatures, while syngas is obtained from glycerol pyrolysis at higher temperatures in the second one. The model is also tested against experiments on combustion of droplets of propanol-glycerol mixtures.