Field-amplified stacking injection-capillary electrophoresis (FASI-CE) applied for the first time to the study of dental materials is demonstrated in this report. CE was used to separate methacrylic acid from the other degraded components. Due to the background electrolyte being weakly basic and methacrylic acid being negatively charged, in-capillary enrichment of the analyte was achieved by FASI. A detection limit of less than 50 ppb was obtained with good reproducibility (relative standard deviation < 3%). The method was applied to the analysis of four commercially available dental composites. Results showed that FASI-CE was effective in monitoring the fabrication process and product quality of restorative materials fabricated from methacrylate-based composites by analyzing the amount of methacrylic acid released from the residual methacrylate monomers.