Ordered and disordered mesoporous silicas have been synthesized through an assembly of non-ionic decaoxyethylene cetyl ether [C 16 (EO) 10 ] and a tetramethoxysilane silica source by variation of the pH value of the synthesis gel. The structure, texture and morphology of the mesoporous silicas, synthesized with concentrated and diluted surfactant solutions, have been discussed from the perspective of silicaÕs chemistry upon a variation of pH values of the synthesis gel (micellar solution). With concentrated surfactant solutions (50 wt%), disordered compounds are obtained in a range of pH from 2.0 to 7.0 (micellar solution). As the pH increases, however, the pore size distributions (PSD) become broader and bimodality appears due to the micelle-templated silica (MTS) mesopores and openings arising from silica dissolution-reprecipitation processes. Also, the MTS pores expand due to a change in conformation of the surfactant hydrophilic head upon pH increase. On the other hand, diluted surfactant solutions (10 wt%) lead to ordered materials in a pH range from 2.0 to 7.0 (synthesis gel). The PSD remain very narrow but interparticular porosity appears and the morphologies undergo deep changes from toroids, gyroids and ropes to aggregates of very small particles with increasing pH.