Laminar flame propagation of branched hexene isomers/air mixtures including 3,3-dimethyl-1-butene (NEC6D3), 2,3-dimethyl-1-butene (XC6D1) and 2,3-dimethyl-2-butene (XC6D2) was investigated using a high-pressure constant-volume cylindrical combustion vessel at 1–10 atm, 373 K and equivalence ratios of 0.7–1.5. The measured laminar burning velocity (LBV) decreases in the order of NEC6D3, XC6D1 and XC6D2, which indicates distinct fuel molecular structure effects. A kinetic model was constructed and examined using the new experimental data. Modeling analyses were performed to reveal fuel-specific flame chemistry of branched hexene isomers. In the NEC6D3 and XC6D1 flames, the allylic CC bond dissociation reaction plays the most crucial role in fuel decomposition under rich conditions, while its dominance is replaced by H-abstraction reactions under lean conditions. The H-abstraction and H-assisted isomerization reactions are concluded to govern fuel consumption in the XC6D2 flame under all investigated conditions. Both C0C3 reactions and fuel-specific reactions are found to be influential to the laminar flame propagation of the three branched hexene isomers. Fuel molecular structure effects were analyzed with special attentions on key intermediates distributions and fuel-specific reactions in all flames. Due to the formation selectivity of key intermediates such as 2-methyl-1,3-butadiene and 2,3-dimethyl-1,3-butadiene, the production of reactive radicals especially H follows the order of NEC6D3 > XC6D1 > XC6D2, which results in the same order of fuel reactivities and LBVs.