In this work, we have developed a chemical procedure enabling the preparation of highly ordered and vertically aligned mesoporous silica films containing selected contents of silver ions bonded inside the mesopore channels via anchoring propyl-carboxyl units. The procedure involves the electrochemically assisted self-assembly co-condensation of tetraethoxysilane and (3-cyanopropyl)triethoxysilane in the presence of cetyltrimethylammonium bromide as a surfactant, the subsequent hydrolysis of cyano groups into carboxylate ones, followed by their complexation with silver ions. The output materials have been electrochemically characterized with regard to the synthesis effectiveness in order to confirm and quantify the presence of the silver ions in the material. The mesostructure has been observed by transmission electron microscopy. We have pointed out that it is possible to finely tune the functionalization level by controlling the co-condensation procedure, notably the concentration of (3-cyanopropyl)triethoxysilane in the synthesis medium.