Multireference configuration interaction calculations are carried out for ground and excited states of dichloromethanol, Cl₂CHOH, to investigate two important photofragmentation processes relevant to atmospheric chemistry. Five low-lying excited states (1¹A″, 2¹A′, 1³A″, 2³A″ and 1³A′) in the energy range between 6.4 and 7.5 eV are found to be highly repulsive for C–Cl elongation, leading to ClCHOH (X²A) and Cl (X²P). Photodissociation along the C–O bond resulting in CHCl₂ (X²A′) and OH (X²Π) has to overcome a barrier of about 0.5 eV because the low-lying excited states 1¹A″, 1³A′ and 1³A″ become repulsive only after the C–O bond is elongated by about 0.3 Å.