Under microwave irradiation, iron-substituted polyoxotungstates (Fe-POMs) catalyze cyclohexane oxygenation to A/K oil with 90–95% selectivity, unmatched turnover frequencies (40–400 h1), and multi-turnover regime (>1000 TON). Such a rapid reaction protocol allowed the screening of so-called inorganic Fe-synzymes with 1 – 4 nuclearity, including a family of Krebs-type isostructural complexes. Product distribution, kinetic analysis, mechanistic probes and fitting calculations, are consistent with a radical chain oxidation propagated by Fe-catalysed decomposition of organic peroxides which ultimately depends on the redox-properties and structural arrangement of the iron moiety within the POM cage.