Sulfuric acid aerosols produced in the stratosphere following massive volcanic eruptions possess a mass‐independent sulfur isotopic signature, acquired when volcanic SO2 experiences UV photooxidation. The volcanic data are consistent with laboratory SO2 photooxidation experiments using UV light at 248 nm (maximum absorption of ozone), whereas sulfur isotopic anomalies previously observed in Archean samples are consistent with photodissociation at 190–220 nm. A mechanism of SO2 photooxidation, occurring in the early stage of a stratospheric volcanic plume, in the range of 220–320 nm (weak band absorption of SO2), is also proposed. Since mass‐independent sulfur isotope anomalies in stratospheric volcanic sulfate appear to depend on the exposure of SO2 to UV radiation, their measurements might therefore offer the possibility to determine the degree of UV penetration in the ozone‐absorption window for the present and past atmospheres. They can also be used to determine the stratospheric or tropospheric nature of volcanic eruptions preserved in glaciological records, offering the possibility to reassess the climatic impact of past volcanic eruptions.