The potential energy profiles, governing the dissociation of acrylic acid (CH2CHCOOH) to CH3CH + CO2, CH2CHOH + CO, CH2CH + COOH and CH2CHCO + OH in the ground as well as in the excited singlet and triplet states, have been determined using different ab initio quantum chemical methods with a correlation-consistent atomic natural orbital basis set of cc-pVDZ. The most probable mechanism leading to different products is characterized on the basis of the obtained potential energy surfaces of the dissociation and the crossing points of the surfaces.