We present a density functional study of the structure and dynamics of solid acetic acid. Our calculations are based on density functional theory combined with molecular dynamics, within the Car-Parrinello scheme. The computed structure of the acetic acid crystal, optimized without symmetry constraints, is in very good agreement with the experiment and reproduces the changes in the intramolecular structure when going from the gas phase to the solid. The cell parameters of the experimental structure are also well reproduced. Cooperative effects along the molecular chains building the crystal are found to be small (1.2 kcal/mol), although larger than it had been previously estimated. The anti conformation of the COOH fragment leads to a stable structure up to 250 K, with an energy of only 3 kcal/mol above that of the known syn form. The energy barrier associated with the most likely pathway for the syn to anti conformations, involving proton transfer along the OH . . .O units (<5.8 kcal/mol) is much smaller than the experimental barrier for the syn/anti isomerism in gas phase and in solution. Intramolecular and intermolecular reorganizations upon change to the anti structure are analyzed. Overall, our results pinpoint the anti form as a good candidate for a possible acetic acid polymorph.