A kinetic and mechanistic study of nitro decarboxylation of α,β-unsaturated acids (USA) has been taken up by Blau's yellow complex [Fe(III) nitrate–Bipy] in polyethylene glycol (PEG)–acetonitrile media. Kinetics of the reactions indicated a rate law: rate = ab[Fe (III)][Bipy][USA]/(1 + b [Bipy]), that represents the Michaelis–Menten type mechanism. Reaction rates are significantly influenced by the structural variation and concentration of PEG. The mechanism of PEG-mediated reaction was explained through the formation of more active [PEG bound Fe(III) nitrate–Bipy species] than [Fe (III) nitrate–Bipy] itself. Formation of [PEG bound Fe(III) nitrate–Bipy species] could be due to the interaction of polyoxyethylene glycolate moiety with [Fe (III) nitrate–Bipy species] in the lines of nonionic micellar interactions.