This work represents a detailed investigation of combustion and oxidation of methyl-3-hexenoate (CAS Number 2396-78-3), including experimental studies of combustion and oxidation characteristics, quantum chemistry calculations and kinetic model refinement. Following experiments have been carried out: Speciation measurements during oxidation in a jet-stirred reactor at 1 atm; chemical speciation measurements in a stoichiometric premixed flame at 1 atm using molecular-beam mass-spectrometry; ignition delay times measurements in a shock tube at 20 and 40 bar; and laminar burning velocity measurements at 1 atm using a heat-flux burner over a range of equivalence ratios. An updated detailed chemical kinetic mechanism for methyl-3-hexenoate combustion based on previous studies was proposed and validated against the novel experimental data and the relevant data available in literature with satisfactory agreement. Sensitivity and reaction pathway analyses were performed to show main decomposition pathways of methyl-3-hexenoate and underline possible sources of disagreements between experiments and simulations. (C) 2020 The Combustion Institute. Published by Elsevier Inc. All rights reserved.