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Iron(IV)-corrole complexes were first investigated as catalysts for olefination of aldehydes with ethyl diazoacetate in the presence of triphenylphosphine. Efficient olefination of aromatic aldehydes with high trans-selectivity was observed, showing iron corrole is a new kind of promising catalyst for olefination reaction. Transformation of the phosphazine to ylide by iron(IV) corrole was proved to be the key step in the present system.