The dissociative photoionization of methyl vinyl ketone (MVK), an important intermediate in the atmospheric oxidation of isoprene, has been studied by photoelectron photoion coincidence spectroscopy. In the photon energy range of 9.5-13.8 eV, four main fragment ions were detected at m/z 55, 43, 42, and 27 aside from the parent ion at m/z 70. The m/z 55 fragment ion (C₂H₃CO⁺) is formed from ionized MVK by direct methyl loss, while breaking the C–C bond on the other side of the carbonyl group results in the acetyl cation (CH₃CO⁺, m/z 43) and the vinyl radical. The m/z 42 fragment ion is formed via a CO-loss from the molecular ion after a methyl shift. The lightest fragment ion, the vinyl cation (C₂H₃⁺ at m/z 27), is produced in two different reactions: acetyl radical loss from the molecular ion and CO-loss from C₂H₃CO⁺. Their contributions to the m/z 27 signal are quantified based on the acetyl and vinyl fragment thermochemical anchors and quantum chemical calculations. Based on the experimentally derived appearance energy of the m/z 43 fragment ion, a new, experimentally derived heat of formation is proposed herein for gaseous methyl vinyl ketone (Δ_fH_0K = -94.3 ± 4.8 kJ mol^-1; Δ_fH_298K = -110.5 ± 4.8 kJ mol^-1), together with cationic heats of formation and bond dissociation energies.