Abstract VUV photodissociation of gaseous acetic acid was studied in the 6–23 eV range using synchrotron radiation excitation, photofragment fluorescence spectroscopy and mass spectrometry. OH (A-X), CH (A,B-X) and H-Balmer emissions were observed. Their relative intensities were studied by fluorescence excitation spectroscopy. The fluorescence quantum yield for OH emission has a maximum of 0.9% at 13.3 eV photoexcitation, dropping to 0.5% at 20 eV; that for CH (A-X) is 0.35% at 16 eV and 0.4% at 20 eV. Photoionization mass spectra (PIMS) of CH 3COOH were measured and the appearance energies of the principal photoions were determined. IE(CH 3COOH) = 10.58 ± 0.02 eV is 40–60 meV lower than previous PIMS values. Dissociative ionization reaction channels are discussed in detail. The results call into question previous determinations of the heat of formation and ionization energy of the acetyl radical. A new pathway is suggested for the formation of HCO +, and the assignments of the m/ z = 16, 28 and 31 ions are clarified. The formation of CH 3 + at threshold is shown to involve carbon–carbon bond rupture and a potential energy barrier. The results of this study are used to discuss aspects of astrophysical observations involving the parent and fragment species.