The autoignition chemistries of the olefins 1-butene, 2-butene, isobutene, 2-methyl-2-butene, and 1-hexene and their corresponding paraffins were examined in a motored, single-cylinder engine by measuring stable intermediate species and performing heat-release analyses. The same engine conditions were used for each olefin-paraffin pair, and compression ratio was varied to affect different levels of chemical activity.Paraffin autoignition chemistry is dominated by hydrogen abstraction from the fuel, followed by the intramolecular alkylperoxy isomerization mechanism. Olefin autoignition chemistry differs markedly being controlled by radical addition to the double bond. Hydroxyl radical addition is followed by oxygen addition to the adjacent radical site, followed by scission forming two carbonyls. Hydroperoxyl radical addition yields an epoxy directly.Experimental measurements for each olefin-paraffin pair are compared with each other and with literature values. The measurements for all olefins and all paraffins are consolidated, and the controlling autoignition chemistries derived from the species measurements are discussed and compared.