Silver diamine fluoride (Ag(NH₃)₂F) arrests caries but stains teeth black. To overcome this drawback, we applied ammonium hexafluorosilicate (AHF; (NH₄)₂SiF₆) and observed changes in the color and structure of demineralized enamel and dentin of extracted primary teeth. Enamel and dentin were demineralized in 10% EDTA solution for 90 s followed by 35% phosphoric acid gel for 60 s, then soaked in AHF solution for 60 s. Before analysis by scanning electron microscopy (SEM) and energy-dispersive X-ray spectrometry (EDS), enamel and dentin were demineralized in 10% EDTA for 90 s. Teeth were divided into 4 groups according to AHF application and artificial saliva immersion status and then examined. The data were statistically analyzed using one-way ANOVA and Fisher's PLSD test at a significance level of P < 0.05. AHF treatment did not cause visible discoloration. Enamel prisms and dental tubules appeared by demineralization were covered with precipitates by AHF application. A sphere-filled membranous structure was observed in the saliva immersion groups. EDS analysis showed that AHF application had no effect on enamel; however, F% and Ca/P ratio were significantly higher on dentin surfaces after AHF application without artificial saliva immersion. Further study on arresting caries treatment is required. (J Oral Sci 54, 267-272, 2012)