Deep-UV photolysis (either 165 or 185 nm) of surface hydroxy groups leads to homolytic OH bond-cleavage with the generation of oxyl radicals that can initiate the room-temperature radical-chain methane activation. Whilst in the absence of oxygen, radical coupling reactions to give low-molecular-weight alkanes are observed in the gas phase, the presence of some oxygen quenches these radicals and increases the selectivity towards C1 oxygenates (methanol, formaldehyde, and formic acid species). The nature of the solid influences the efficiency of the photochemical process and the distribution between products in the gas and solid phases. Using Beta-, delaminated ITQ2 and ITQ6, and medium-pore ZSM5 zeolites, mesoporous MCM41 silicates, and non-porous TiO2, we observed that confinement and porosity increased the proportion of C1 oxygenates adsorbed onto the solid and reduced the contribution of the gas-phase products. In addition, the presence of aluminum in the zeolite framework, which is responsible for the generation of acid sites, increased overoxidation of methanol and methoxy groups into formaldehyde and formic acids. For a given amount of methane and unchanged photolysis conditions, the conversion increased with the amount of the solid used as photocatalyst. In this way, methane conversions of up to 7 % were achieved for the 185 nm photolysis of methane for 1 h with a 76 MJ mol−1 energy consumption.