The　reaction　kinetics　of　alkenes　+　hydroperoxyl　(H2)　system　is　of　importance　to　low/intermediate　temperature　chemistry　of　alkanes.　This　work　is　a　follow　up　of　our　previous　study　on　3-hexene　+　H　[1],.　The　rate　coefficients　were　determined　using　the　canonical　variational　transition-state　theory.　Results　revealed　that　the　asymmetric　geometry　of　the　H2　radical　generated　numerous　reaction　sub-channels.　The　rate　coefficients,　with　a　conservative　uncertainty　(factor　of　5),　were　obtained　to　develop　the　detailed　chemical　mechanism　of　3-hexene.　Additionally,　potential　energy　surface,　minimum　reaction　path,　adiabatic　ground-state　energy,　and　activation　free　Gibbs　energy　change　(ΔG)　calculations　were　also　performed.　©　2020　Elsevier　Ltd