More acidic sulfated metal oxides (SMO) such as SO4 2-/ZrO2 and SO4 2-/TiO2 catalyzed the methoxymethylation of alcohols with dimethoxymethane at ambient temperature to achieve a product yield of greater than 90% within a few hours. The reaction displayed a significant steric effect on the product yield with a preferential order of primary alcohol > secondary alcohol tertiary alcohol. The observed steric effect might result from the repulsion between the bulky alkyl group in the alcohol and the two methoxy groups in the protonated dimethoxymethane (oxonium ion).