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Methyl vinyl ketone (MVK), a volatile compound with photochemical activity, has received considerable attention in the fields of environmental chemistry and atmospheric chemistry. We explored the conformational stabilities of MVK in the neutral S0 and the cationic D0 states using conformer-specific vacuum ultraviolet mass-analyzed threshold ionization (VUV-MATI) spectroscopy, which provided identifiable vibrational spectra for cationic MVK conformers. Based on the origin bands of the two individual conformers of MVK identified in th