The biologically important reaction of nitrosobenzenes with thiols has been investigated in 2-propanol solution at room temperature, experimental conditions which allow for the detection and characterization of key intermediates. Final stable products of such complex reactions include azoxybenzenes and anilines, formed in relative proportions and at a rate which depend on the reagents initial molar ratio. A detailed description of the reaction of 4-chloronitrosobenzene with benzenethiol in 2-propanol was achieved by means of (1)H NMR in situ analysis. The reaction is initiated by rapid and quantitative coupling of the two reagents into a covalent adduct, an N-hydroxysulfenamide (N(OH)S), which decays to N-(4-chlorophenyl)hydroxylamine. This second intermediate is then converted via competing paths to 4,4'-dichloroazoxybenzene and to N-(4-chlorophenyl)benzenesulfenamide (4-ClC(6)H(4)NHSPh), which in turn decays to 4-chloroaniline. Interestingly, sulfinamides (ArNHS(O)R), major products of the reaction in aqueous media, do not form in 2-propanol.