The degree of polymerization for dimethacrylate resin-based materials (BisGMA, TEGDMA, UDMA, HEMA) ranges from 55 to 75%. Literature data indicate that polymerization efficacy depends, among other factors, on the type of methacrylate resin comprising the material. The aim of this study was to evaluate the polymerization efficacy of four dental cement materials characterized by different polymerization mechanisms using FTIR analysis. In the present study, the FTIR method was adopted to analyze the degree of polymerization efficacy of four resin-based dental cement materials, two of which were self-cured and two were dual-cured cements. The IR spectral analysis was performed 24 h after the polymerization of the cementitious material. RelyX ARC cement exhibits the lowest polymerization efficacy (61.3%), while that of Variolink II (85.8%) and Maxcem Elite is the highest (90.1%). Although the efficacy of self-cured cements appears to be superior, the difference is not statistically significant (p = 0.280). Polymerization efficacy largely depends on the chemical structure of the material in terms of the presence of a particular methacrylate resin and less on the polymerization mechanism itself, i.e., whether it is a self-cured or dually cured dental cement. Thus, in clinical practice, cementitious materials with a higher proportion of TEGDMA compared with BisGMA are recommended.