The reaction of acetic acid with stoichiometric and reduced runic TiO2(011) single-crystal surfaces has been studied under dark and UV illumination conditions. The surface coverage after the dissociative adsorption of acetic acid with respect to Ti was found to be 0.55. Monitoring XPS Ti, O, and C lines revealed that the surface population decreased incrementally with temperature up to 650 K. The decrease in the slope of both the -CH3- and -COO- XPS peaks was not monotonic and followed two slopes in agreement with TPD results. The first channel involves the removal of surface acetates to acetic acid by recombinative desorption, and the second mainly involves dehydration to ketene. UV-light illumination was conducted at 300 K in the absence and presence of molecular oxygen at different pressures: in the 10(-6)-10(-9) Torr range. Acetate species were found to decrease with illumination time, and their decrease is seen to be dependent on the oxygen pressure. Plausible decomposition pathways are presented. Deliberately reducing the surface by electron bombardment prior to the adsorption of acetic acid did not affect the photoreaction rate within the experimental limits.