Mesoporous silica materials with different pore structures and sizes have been used for supporting aryl sulfonic acid catalytic sites via a postsynthetic grafting approach. The synthesized materials have been evaluated in the solventless acid-catalyzed self-condensation of cyclohexanone (CHO) to obtain the corresponding C12 adducts. These compounds display great potential as oxygenated fuel precursors as they can be transformed into jet fuel range alkanes in a subsequent hydrodeoxygenation process. Inthis work, the synthesized catalysts have displayed high selectivity values toward monocondensed compounds (>95%), thus limiting the formation of undesired heavier condensation products, together with CHO conversion values in the range 20−40% after 2 h of reaction at 100 °C. The structural and textural properties of the supports play an important role in the catalytic performance. Moreover, the activity per acid center is correlated with the textural properties of the supports, indicating that a lower surface density of the anchored aryl sulfonic groups affords an improvement in their specific activity. Finally, the benefit of using supports with large pore sizes and open structures, which limit the fouling of the catalysts by organic deposits, is demonstrated in a stability and reusability test.