•Super-microporous zeolite Fe–MFI was prepared via template method.•Potassium hexacyanoferrate as an iron source in the syntheses.•The iron ions incorporated onto the zeolite network in tetrahedral coordination.Zeolite Fe–MFI possessing super-micropores has been synthesized by a direct hydrothermal method using potassium hexacyanoferrate(III) as the iron source. The results show that the material has a highly crystalline MFI zeolite structure, displaying a regular structure with ca. 0.7–1.5 nm in pore diameter. X-ray absorption spectroscopy results indicated that the iron was present in the form of tetrahedrally coordinated Fe3+ ions incorporated on the zeolite network. The super-microporous Fe–MFI exhibited good catalytic performance in the hydroxylation of phenol by H2O2.Scanning electron microscope provided evidence that the synthesized Fe–MFI has a highly crystalline MFI structure. Nitrogen sorption isotherms of the sample showed the presence of super-micropores.