The photochemical action of arylazo sulfones under visible light irradiation has recently gained considerable attention for the construction of carbon-carbon and carbon-heteroatom bonds in organic synthesis. The inherent dyedauxiliary group (-N2SO2R) embedded in the reagent is responsible for the absorption of visible light even in the absence of a photocatalyst, additive or oxidant, leading to the generation of three different radicals, viz. aryl (carbon-centred), sulfonyl (sulphur-centred) and diazenyl (nitrogen-centred) radicals, under different reaction conditions. Encountering a reagent with such a versatile behaviour is quite rare, which makes arylazo sulfones a highly interesting class of compounds. The mild reaction conditions under which these reagents can operate are an added advantage. Recently, they are also being used as non-ionic photoacid generators (PAGs), electron acceptors, and hydrogen atom transfer (HAT) and imination reagents in a number of synthetic transformations. They have displayed substantial damaging effect on the structure of DNA in the presence of light which can lead to their use as phototoxic pharmaceuticals for cancer treatment. Moreover, their photochemistry is also being exploited in polymerization reactions (as photoinitiators) and in materials chemistry (surface modification).