Purpose: This work aims to study the erosion on restorative materials and on surrounding dentin. Fifty root dentin samples were obtained from bovine incisors. Methods: Twenty samples were not restored and thirty received cavity preparations. Samples were assigned to five groups: G1, G2: sound dentin (D); G3: composite resin (CR); G4: resin‐modified glass‐ionomer cement (RMGIC); G5: glass‐ionomer cement (GIC). The samples of groups 2–5 were submitted to six cycles (demineralization–remineralization). Samples were analyzed by micro energy‐dispersive X‐ray fluorescence spectrometry (μ‐EDXRF) and by scanning electron microscopy (SEM). Results: Mineral loss was greater in G2 samples than in RMGI > CR > GIC > D (control). SEM images showed pronounced dentin demineralization in groups 2 and 4. The acid erosion has a significant effect on mineral loss (Ca and P) of root dentin without restoration. Conclusions: Composite resin had the best chemical resistance to erosion among all the materials. Fluoride contained in GIC seemed to cause some protection, however, with material degradation. Chemical interaction of tooth‐colored dental materials with root dentin could be assessed by μ‐EDXRF. Microsc. Res. Tech. 75:703–710, 2012. © 2011 Wiley Periodicals, Inc.