AbstractTitania‐silica immobilized Co(salen) complexes containing the heterobinuclear site were prepared by the sol–gel method for the catalytic synthesis of methyl N‐phenylcarbamate (MPC) by the oxidative carbonylation of aniline. It was found that the Ti:Si mole ratio had an important effect on the catalytic performance of Co(salen) complexes. When the Ti:Si ratio was 0.1, titania‐silica supported Co(salophen) showed the best catalytic activity. Under the reaction conditions, Co(salophen)/TS‐0.1, 0.5 g, aniline 11 mmol, methanol 25 ml, KI 2.2 mmol, CO:O2 9:1, total pressure 6 MPa, 150 °C, 3 h, the conversion of aniline and the selectivity of MPC were 60.7 and 88.1%, respectively. The XRD studies showed that titania was highly dispersed in the silica matrix. Co(salophen)/TS‐0.1 was reused five times with no significant loss of the activity, and no Co leaching was observed in the reaction. Copyright © 2009 John Wiley & Sons, Ltd.