Ethylene glycol (EG) and its mono-methyl ether (MME) were synthesized directly from ethylene and hydrogen peroxide under mild conditions using Al–TS-1 as the bifunctional catalyst. The progressive incorporation of Al into the framework increased the catalytic capacity of Al–TS-1 until a maximum was reached (SiO 2 /Al 2 O 3 molar ratio: 504), whereas further Al incorporation decreased the catalytic activity to even lower values than in TS-1. Under the optimum conditions, the conversion and utilization of H 2 O 2 reached 95% and 90%, respectively, while the total concentration of EG and MME reached to above 10wt.%.