ABSTRACT Methanol, which is one of the most abundant organic molecules in the interstellar medium, plays an important role in the complex grain surface chemistry that is believed to be a source of many organic compounds. Under energetic processing such as ultraviolet (UV) photons or cosmic rays, methanol may decompose into CH4, CO2, CO, HCO, H2CO, CH3O and CH2OH, which in turn lead to complex organic molecules such as CH3OCHO, CHOCH2OH and HOCH2CH2OH through radical recombination reactions. However, although molecular oxygen and its detection, abundance and role in the interstellar medium have been the subject of many debates, few experiments on the oxidation of organic compounds have been carried out under interstellar conditions. The present study shows the behaviour of solid methanol when treated by UV light and thermal processing in oxygen-rich environments. Methanol has been irradiated in the absence and presence of O2 at different concentrations in order to study how oxidized complex organic molecules may form and also to investigate the O-insertion reaction in the C–H bound to form methanediol HOCH2OH through a CH3OH + O(1D) solid-state reaction. The adding of O2 in the thermal and photochemical reaction of solid methanol leads to the formation of O3, H2O and HO2, in addition to three main organics, HCOOH, CHOCHO and HOCH2OH. We show that in an O2-rich environment, species such as CO, CH4, HCO, CH3OH and CHOCH2OH are oxidized into CO2, CH3OH, HC(O)OO, HOCH2OH and CHOCHO, respectively, while HCOOH might be formed through the H2CO + O(3P) → (OH + HCO)cage → HCOOH hydrogen-abstraction reaction.