The hardening of modified polyacid composite resins (compomers) and glass-ionomers have been studied using infrared spectroscopy. The acid-base reaction in Ketac-fil, a glass ionomer, was followed by the ratio between the COOH band located around 1715 cm⁻¹ and that corresponding to COO⁻ located around 1570 cm⁻¹. The combination of infrared analysis and band narrowing treatments enable us to propose in the glass-ionomer two maturation steps. First, a very rapid equilibrium acid-base related, and second the cross-linking of polycarboxylate with the metal ions present in the cement. In compomers, a new reaction has been described involving polymerization induced by free radicals besides the two steps associated with the acid-base reaction. Using infrared spectroscopy and band narrowing techniques, it is shown that water is essential to complete the hardening process but no acid-base reaction is produced since the COO⁻ band does not appear. The reaction associated with free radicals could be described as a polymerization of methacrylate monomers together with an aqueous dilution of the filling particles releasing different metal cations that would chelate with the polymer molecules to form a macromolecular structure.