The regioselective addition of aryl and aryldiazenyl substituents to olefinic substrates can be described as carbodiazenylation. In this report we present our final results relating to this unique type of radical functionalization reaction, which has now been developed into a convenient, versatile and highly effective synthetic method. Starting from an investigation into rate constants for the addition of aryl radicals to monosubstituted, non-activated olefins, this key step is shown to be both fast and selective in mixtures of dimethyl sulfoxide and water. The by-products obtained in earlier reactions reveal that the main complication of carbodiazenyl-