New Lewis acid AlTf-UVM-7 catalysts with bimodal pore system and different Si to Al ratios were prepared in a two-step synthesis in which triflic acid (Tf) was incorporated into previously synthesized mesoporous aluminum-containing silica. The Al incorporation inside the pore walls was carried out through the Atrane method. The characterization of the resulted catalysts showed that the triflic acid treatment step did not damage the texture or the structure of the catalysts. These materials were used as green catalysts for the etherification of fatty alcohols and the conversion of ethylene glycol (EG) with n-octanol resulting in mixtures of short ethoxylated structures with a large distribution of C8E1-C8E3 products. The process occurred with high conversions of ethylene glycol and high selectivities to ethoxylated products. Recyclable experiments showed the catalysts are stable and the reuse occurred without changes in the chemical composition. (C) 2009 Elsevier B.V. All rights reserved.