The radiolysis of liquid and boiling hexafluoroacetylacetone was studied. The structure of the main radiolysis products indicates the predominance of C–CF3 and C–F bond cleavages. Ten compounds are formed, including monoketones, trifluoroacetic acid, keto alcohols, and tautomeric tetraketones. Carbon monoxide is the main gaseous product and its yield increases under boiling conditions. The initial yield of hexafluoroacetylacetone degradation is 0.29 ± 0.2 and 0.32 ± 0.2 µmol J-1 at 293 and 343 K, respectively. No accumulation of free HF is observed at low doses. The products of radiolysis are less diverse than in acetylacetone, which is due to the increased “cage” effect, the increase in the Onsager radius and the ability of trifluoromethyl groups to dissipate excitation energy.