This study aimed to evaluate the extension of enamel demineralization around the margin of restorations after immersion in cariogenic solution, in an attempt to define the role of new restorative materials in preventing secondary caries formation. For this purpose, enamel microhardness was measured. Twelve class V restorations in human extracted third molars were prepared in vitro and immersed in a demineralizing solution (lactic acid, pH 4.5) at 37 degrees C for 3 days to simulate the formation of secondary caries and its effect on the marginal integrity of composite restorations. The restorative systems tested in the study were Scotchbond 1 + Z 250 (group A), ABF + APX (group B), Fuji IX (group C), SE Bond + APX (group D), and Scotchbond 1 + F 2000 (group E). The microhardness was measured close to the margin of restoration (marginal exposed enamel), at 2.0 mm from the margin (exposed enamel), and at approximately 4 mm from the margin in a varnish-covered enamel area (protected enamel). Five measurements were made on each site at 20, 40, 60, 80, and 100 microm depth from the external enamel surface. Exposed enamel and marginal exposed enamel were greatly affected by the cariogenic solution, as confirmed by the high rate of demineralization. The marginal exposed enamel showed a higher rate of demineralization than the exposed enamel, as demonstrated by the lowest microhardness values. The materials that claimed fluoride release did not prevent any type of enamel marginal alteration. This study revealed that enamel close to the margin of restoration may be rapidly affected by secondary caries formation when immersed in a demineralizing-cariogenic solution and that fluoride-releasing materials are unable to reduce the marginal demineralization processes. These demineralization processes may be responsible for marginal secondary caries and for restoration failures.