Abstract About twenty years ago, in an effort to transform natural rubber into gutta-percha, Meyer and Ferri irradiated a solution of Hevea in cyclohexane with ultraviolet light, but were unable to detect any cis-trans isomerization in polyisoprene. Later, Ferri showed that treatment of both Hevea and Gutta with certain chemicals, such as chlorostannic acid and titanium tetrachloride, gave rise to closely resembling products which were considered at the time to have structures intermediate between the two geometric forms of naturally-occurring polyisoprene. These resulting polymers were, however, crosslinked in the course of chemical treatment and probably also cyclized, so that in the light of present knowledge about the cyclizing tendencies of the materials employed, this change cannot be regarded as a genuine interconversion of cis and trans double bonds. No true instance of cis-trans isomerization unaccompanied by other structural changes has been reported heretofore for a high polymer, except for the polyenes which are conjugated structures of relatively very low molecular weight. This communication reports the successful transformation of the cis-1,4 units in polybutadiene into corresponding trans units by means of ultraviolet irradiation in the presence of a suitable sensitizer, which may be any one of a wide variety of organic bromine or sulfur compounds. Surprisingly, this isomerization could not be induced in natural rubber.