The polymerization process of the dual-cured resin cement AllCem (FGM, Joinvile, Brazil) was investigated by unilateral nuclear magnetic resonance (NMR-MOUSE) and electron paramagnetic resonance (EPR). The NMR experiment allows measurements of the mobile monomers as function of time and depth, while real-time X-band EPR monitoring gives information about the concentration of free radicals. The monomer concentration instantly decays for photo-cured samples, but it remains constant about similar to 4 min for self-cured samples before starting to decrease. For the self-cured sample, the concentration of free radicals suddenly decreases to zero and then reappears with a strongly increasing rate. Models for the polymerization kinetics of each initiation protocol are proposed, giving insight into the polymerization process of the dual-cured resin cement.