Muoniated free radicals have been detected in muon-irradiated aqueous solutions of acetone at high temperatures and pressures. At temperatures below 250 °C, the radical product is consistent with muonium addition to the keto form of acetone. However, at higher temperatures, a different radical was detected, which is attributed to muonium addition to the enol form. Muon hyperfine coupling constants have been determined for both radicals over a wide range of temperatures, significantly extending the range of conditions under which these radicals and the keto−enol equilibrium have been studied.