Unsaturated monomers containing none, one, or two hydroxy groups were obtained by the reaction of glycerol (1,2,3-trihydroxypropane) with acrylic and methacrylic chloride. The experimental values of the mole fractions of the different monomers were compared with those theoretically obtained by considering different mechanisms involving two or seven kinetic constants. Agreement between the theoretical and experimental results could only be achieved by assuming that the reactivity of the hydroxyl groups changed with the presence of the substituents. The investigation of the radical polymerizations 2,3-dihydroxypropylacrylate (GA) and 2,3-dihydroxypropylmethacrylate (GM) was carried out at several temperatures in water-dioxane solutions. Ultraviolet spectroscopic techniques were used to determine the kinetic constants, and the results were compared with those obtained in the same conditions for methyl acrylate, methyl methacrylate, 2-hydroxyethylmethacrylate, and 2-hydroxyethylmethacrylate. The values of the ratio k(p)/k(t)(1/2) for the methacrylic monomer GM were higher than 0.5 L-1/2 mol(-1/2) s(-1/2) at temperatures between 50 and 65 degreesC. These values exceeded 2 L-1/2 mol(-1/2) s(-1/2) for the acrylic monomer GA, perhaps the highest values reported for this kind of monomer. Electron paramagnetic resonance spectroscopy was also used to study the polymerization of GM. All the polymers were soluble in the reaction mixture until very high conversions, and the gel effect was never detected at monomer concentrations equal to or lower than 1 mol L-1.