Catalytic aerobic epoxidation is a key process for new sustainable systems in the field of hydrocarbon functionalization. The screening of selected Fe-POM catalysts for the aerobic epoxidation has been performed using cis-cyclooctene as model substrate. Our results support a ubiquitous radical chain epoxidation with selectivity up to 66%, TOF in the range 4-50 h(-1) and total turnover number > 7000. FT-IR spectroscopy has been used to assess the stability of the various POM-based catalysts with respect to analogue organic porphyrine ligands. (c) 2006 Elsevier B.V. All rights reserved.