The well-known Stöber method has been widely used to synthesize nonporous silica nanospheres (NPs), however, in the absence of surfactant templates, the synthesis of mesoporous silica nanospheres (MSNs) has not been achieved. Herein, in the absence of organic surfactant templates, by a simple premixing of three components tetraethoxysilane-water-ethanol (TEOS-H2O-EtOH) with a precise molar ratio, the parent silica nanoparticles with a low condensation degree and controlled particle size can be readily obtained. Subsequently, via a simple two-step post-treatment, the obtained MSNs exhibited a high surface area (ca. 500 m2 g-1), accessible mesopores (3.0 nm), and a large pore volume (0.87 mL g-1), similar to those of MCM-41 and SBA-15 silicas. The unique self-templating role of the 'pre-Ouzo' effect of ternary surfactant-free TEOS-H2O-EtOH systems was proposed to understand the formation of mesoporosity.