The gaseous photochemical reaction of n-pentane and sulfur dioxide was studied.A series of gaseous products such as alcohols, ketones, acids, esters and inorganic compound were identified by GC/MS and GC. According to the characters of the compounds and the free radical theory, the free radical mechanism of this gaseous photochemical reaction was suggested. The free radical mechanism was verified directly by means of the gaseous free radicals measured by spin trapping-ESR methods in which PBN was selected as the spintrap.