For the sol–gel synthesis of silica particles under high pH catalytic conditions (pH>12) in water/ethanol solvent, we have deduced that the competing dynamics of chemical etching and sol–gel process can explain the types of silica particles formed and their morphologies. We have demonstrated that emulsion droplets that are generated by adding tetraethyl orthosilicate (TEOS) to a water–ethanol solution serve as soft templates for hollow spherical silica (1–2μm). And if the emulsion is converted by the sol–gel process, one finds that suspended solid silica spheres of diameter of ∼900nm are formed. Moreover, several other factors are found to play fundamental roles in determining the final morphologies of silica particles, such as by variation of the pH (in our case, using OH–) to a level where condensation dominates; by changing the volume ratios of water/ethanol; and using an emulsifier (specifically, CTAB)