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Chemists are now moving away from volatile, environmentally harmful, and biologically incompatible organic solvents. With its low cost, ready availability, and capacity to remove environmentally unfriendly by-products, water and alternative biocompatible reaction media such as ionic liquids are obvious replacement. Recent advances in free radical chemistry in water have expanded the versatility and flexibility of homolytic bond formations in aqueous media and ionic liquids. This special Hot Topic issue highlights the substantial progress, which has been made in the last decade to “tame” the reactive free radical species in aqueous phase reaction and alternative media. The issue describes conventional radical reactions in organic and aqueous media and their applications. There are 2 review articles in the on radical reactions in broad range of free radical transformation in aqueous and alternative media, such as ionic liquids, solid phase, microwaves and supercritical CO2, in the issue collate the unique application and tutorial hints for designing the optimum free radical reaction. Article by Lykakis et al., describes the decatungstate W10O32 4- catalyzed photooxygenation of cumenes in the presence of molecular oxygen and triethylsilane representing an important potential for free radical reactions in synthesis. Article by Nanni et al., focuses on radical additions of thiols to alkenes and alkynes in ionic liquids, which is adding an extra dimension to the scope of free radical reactions in alternative media. Article by Grabovskiy et al., describes investigation both synthetic and mechanistic of 5-Hydroxy-6-methyluracil, an efficient scavenger of peroxyl radical in water. The article by Johnson and Chen et al. focuses on investigation of the broad range of free radical transformation in beta-cyclodextrin based molecular reactors and polyHIPEs as alternative reaction media. It shows that, armed with an elementary knowledge of kinetics and some common sense, it is possible to harness radicals into tremendously powerful tools for solving synthetic problems and broad range of applications. The issue is a valuable and informative entry for growth and development of green free radical chemistry in aqueous and alternative media.