Systems and methods are provided for direct methane conversion to methanol. The methods can include exposing methane to an oxidant, such as O2, in a solvent at conditions that are substantially supercritical for the solvent while having a temperature of about 310° C. or less, or about 300° C. or less, or about 290° C. or less. The solvent can correspond to an electron donor solvent that, when in a supercritical state, can complex with O2. By forming a complex with the O2, the supercritical electron donor solvent can facilitate conversion of methane to methanol at short residence times while reducing or minimizing further oxidation of the methanol to other products.