Most thermochemical methane upgrading technologies suffer from intense energy consumption and low methane conversion due to the high energy barrier and the unfavorable thermodynamics of methane reactions. We developed a photochemical variant of methane halogenation reaction that requires minimum energy input by harnessing solar energy for methane activation and by reacting methane with N-haloimides that generate more oxidative and reactive N-centered imidyl radicals upon excitation. The reaction with N-bromosuccinimide (NBS) afforded methyl and methylene bromides with a selectivity toward methyl bromide of up to 92% at room temperature and atmospheric pressure. A minimum methane loading of 5 equiv relative to N-haloimides furnished results similar to those obtained in the presence of a large excess of methane. A good volumetric productivity of approximately 5 kg (CH3Br).m(-3.)h(-1) was achieved. Interestingly, the first selective iodination of methane at a moderate temperature (35-80 degrees C) to give methyl iodide with 84-96% selectivity was achieved with N-iodosuccinimide (NIS) and N-iodophthalimide.