Purpose: To investigate the chemical polymerization kinetics of commercial dual-curing adhesive systems when used solely or in conjunction with chemically-curing resin cement. Materials and Methods: Four adhesive systems comprising simplified-step adhesives and activators (Prime&Bond NT with Self Cure Activator, Excite DSC, AQ Bond Plus, All-Bond SE) were used. The pH values of the adhesives and adhesive/activator blends were measured. Differential scanning calorimetry (DSC) was used to investigate the extent of the chemical polymerization of the adhesives when used alone or directly intermixed with a chemically-cured resin cement (C&B Cement) for 60 min (n = 5). The data derived from the DSC analysis were statistically compared using one-way ANOVA and the Games-Howell post-hoc test (α = 0.05). Results: All the adhesives were highly acidic; when they were blended with the respective activators, their pH values increased. Neither the adhesive/activator blends nor the adhesive alone/cement mixtures showed any detectable heat generation. The Prime&Bond NT/activator showed delayed heat generation only when intermixed with the catalyst/base paste. The other three adhesive systems produced similar exotherms when intermixed with the catalyst paste alone or with the catalyst/base paste (p > 0.05), but at significantly different maximum rates of polymerization (p 0.05). Significantly shorter induction periods resulted when AQ Bond Plus and All- Bond SE were intermixed with the catalyst/base paste rather than with the catalyst paste alone (p = 0.004). Conclusion: The chemical polymerization occurring at the adhesive system/resin cement interface appears highly dependent on the adhesive system used and may be considerably delayed. Keywords: activator, adhesive, polymerization, resin cement