Mesoporous silicas synthesized by the co-condensation of two and three different silica monomers were synthesized by varying the time intervals between the addition of individual monomers, while the total time interval was kept constant. This resulted in different structural properties of the final silicas, particularly in their porosity and local ordering. One of the obtained samples exhibited an unusual isotherm with two hysteresis loops and its total pore volume was as high as 2.2 cm3/g. In addition, to be thoroughly characterized by a wide range of instrumental techniques, the obtained materials were also employed as the adsorbents and release platforms of a diclofenac sodium (DICL; used here as a model drug). In the case of DICL adsorption and release, differences between the samples were also revealed, which confirms the fact that time control of a monomer addition can be successfully used to fine-tune the properties of organo-silica materials.