The adsorption of dimethyl ether has been studied at its boiling point on a range of silica gels by measurement of adsorption/desorption isotherms and isothermal calorimetric heats of adsorption. Data were determined on gels heat treated at 240, 500, 700, and 900 °C and also on gels impregnated with 0.274% w/w aluminum. On 240 °C gels, heats of adsorption varied from around 20 through 12 to 7 kcal/mole at θ = 0.01, 0.50, and 0.90, respectively. Hysteresis loops are analyzed and the initial adsorption trends explained by hydrogen bond formation between the ether oxygen and surface hydroxy groups. The enhanced amounts of ether adsorbed after aluminum impregnation are explained by the creation of either Brønsted acid sites on gels treated at 240 °C or Lewis acid sites on gels treated at the highest temperatures.