The objective of the study was to gain more understanding on the photopolymerization mechanism and the role of individual monomers in the polymerization behavior of a PAE-based self-etch adhesive system with the presence of HAp and water. The photo-polymerization process of the model adhesive system (2MP/HEMA) was monitored by using real-time attenuated total reflectance Fourier transform infrared (ATR/FT-IR) technique. The effect of monomer ratio, HAp incorporation, and water content were investigated. The degree of conversion (DC) and the polymerization rate (PR) of the adhesives were determined to evaluate the polymerization efficacy. The results showed that the DC and PR increased consistently as the 2MP content increased from 30% to 70%, while they declined drastically as the 2MP content was further elevated to 100%. The incorporation of HAp considerably increased the DC and PR; however, the increase in water content was found to have negative influence on the photopolymerization.