Papain, trypsin and collagenase were used in the experiment for the study of their effects on the demineralization of enamel surface by organic acids in vivo. No effect of any of the enzymes was observed. The use of papain and trypsin in treating tooth surfaces in vitro, no matter whether sodium bisulfite was used, showed no effect on the demineralization of the enamel by mixed organic acids. But, by the analysis of amino acids in the enzyme solutions before and after treating tooth surface, it was shown that some proteinous substances were destroyed. Accordingly, it can be suggested that the enzyme takes no part in the destruction of the inorganic tooth substance.