The methyl esters of 4 individual positional isomers of hydroperoxides, 2 positional isomers of hydroperoxy cyclic peroxides and a 9,16-dihydroperoxide were prepared by autoxidation of methyl linolenate and separated by preparative high pressure liquid chromatography. Isolated hydroperoxide isomers were thermally decomposed and the resulting volatile components analyzed. Each hydroperoxide or hydroperoxy cyclic peroxide isomer yielded characteristic volatile products. The major volatiles from each acyclic hydroperoxide corresponded with those predicted to arise by carboncarbon scission on either side of the corresponding alkoxy radical intermediate and little evidence was found of isomerization between the various positional isomers occurring during the process. A similar mechanism would account for the volatile products obtained from the cyclic peroxides. 2,3-Pentanedione was a significant odor contributor arising from the 13,15-epidioxy-16-hydroperoxide isomer although it was only a minor decomposition product.