The alumina/silica with zinc chloride aerogel alkylation catalyst was obtained using a one step sol-gel synthesis, and subsequent drying with supercritical carbon dioxide. The aerogel catalyst activity was found to be higher compared to the corresponding xerogel catalyst, as a result of the higher aerogel surface area, total pore volume and favourable pore size distribution. Mixed Al–O–Si bonds were present in both gel catalyst types. Activation by thermal treatment in air was needed prior to catalytic alkylation, due to the presence of residual organic groups on the aerogel surface. The optimal activation temperature was found to be in the range 185–225°C, while higher temperatures resulted in the removal of zinc chloride from the surface of the aerogel catalyst with a consequential decrease in the catalytic activity. On varying the zinc chloride content, the catalytic activity of the aerogel catalyst exhibited a maximum. High zinc chloride contents decreased the catalytic activity of the aerogel catalyst as the result of the pores of the catalyst being plugged with this compound, and the separation of the alumina/silica support into Al-rich and Si-rich phases. The surface area, total pore volume, pore size distribution and zinc chloride content had a similar influence on the activity of the aerogel catalyst as was the case of xerogel catalyst and supported zinc chloride catalysts.