2–8 wt % iron has been grafted over SBA-15 and 10 wt % alumina grafted SBA-15 (AlSBA-15) through selective extraction deposition technique using LaFeO3 as iron precursor in acidic solution. DRS-UV spectra confirmed the presence of iron as isolated Fe(III), Fe(III)-clusters and amorphous FeOx oligomers. SEM-EDX mapping, FT-IR, XPS, HR-TEM and 27Al MAS NMR characterisation results confirmed that iron grafted over AlSBA-15 preferentially reside on the alumina. The donor-acceptor interaction of grafted iron ions with alumina atoms displaying Lewis acid properties stabilized iron at higher oxidation state Fe(III+δ). This increased the BE of Fe2p electrons (XPS) and shifted the temperature of iron reduction in 2–8 wt %Fe/AlSBA-15 materials to higher value (600 °C) compared with Fe/SBA-15 (H2-TPR). In arylation of benzene, 8 wt %Fe/AlSBA-15 demonstrated excellent redox catalytic activity with TOF close to homogeneous catalyst and 82 % biphenyl yield. The catalyst demonstrated consistent catalytic performance for 7 cycles. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim