The co-condensation of tetraethoxysilane and an amphiphilic organosilane precursor containing an ammonium part is investigated in presence of different counter-ions. We highlight the morphological versatility offered by such “one pot” synthesis, resulting of the combinatory effects of the addition of tetraethoxysilane and of the nature of the counter-ion involved in the sol-gel process. Indeed, the interactions at the interface governed by the ammonium species affect the shape of the aggregates, making of the counter-ion a critical morphological parameter. The morphology of the particles is also closely linked to the homogeneity of the system. Thereby, using the immiscibility of the tetraethoxysilane/water mixture, we showed that it is possible to get macroporous, blackberry-like or cerasome materials. Oppositely, the use of tetrahydrofuran able to solubilize all the systems leads to monodisperse nanoparticles whose size can be modulated as a function of the involved counter ion.