Components and sulfur isotopic compositions of pyroclastic materials from the 2014 Mt. Ontake eruption were investigated. The volcanic ash samples were found to be composed of altered volcanic fragments, alunite, anhydrite, biotite, cristobalite, gypsum, ilmenite, kaolin minerals, native sulfur, orthopyroxene, plagioclase, potassium feldspar, pyrite, pyrophyllite, quartz, rutile, and smectite, and most of these minerals were likely derived from the acidic alteration zones of Mt. Ontake. The absence of juvenile material in the eruptive products indicates that the eruption was phreatic. The sulfur isotopic compositions of the water-leached sulfate, hydrochloric acid-leached sulfate, acetone-leached native sulfur, and pyrite of the samples indicate that these sulfur species were produced by disproportionation of magmatic SO2 in the hydrothermal system at temperatures of 270–281 °C. This temperature range is consistent with that inferred from the hydrothermal mineral assemblage (e.g., pyrophyllite and rutile) in the 2014 pyroclastic materials (200–300 °C). Except for the sulfur isotopic compositions of anhydrite, which may have been altered by incorporation of sulfate minerals in a fumarolic area with lower sulfur isotopic values into the underground materials during the 1979 eruption, no significant differences in the mineral assemblages and sulfur isotopic compositions of the pyroclastic materials were identified between the products of the 2014 and 1979 Ontake phreatic eruptions, which suggests geochemical similarities in the underlying hydrothermal systems before the 2014 and 1979 eruptions.