A new type of surfactant-free microemulsion (SFME) containing water/ethanol/dichloromethane was constructed, and three microregions water-in-dichloromethane (W/O), bicontinuous (B.C.) and dichloromethane-in-water (O/W) regions were identified. The polarity environment of the SFME was investigated. Solid silica nanoparticle (SSN) was selected as a model nanomaterial to investigate the feasibility of the water/ethanol/dichloromethane SFME for the preparation of nanomaterials. In the O/W SFME region of the microemulsions, uniform spherical solid silica nanoparticles (SSNs) were synthesized. Under the same experimental conditions, they are of smaller particle size and have narrower range of diameter distribution, than the SSNs synthesized from ethanol and water mixture. The effects of tetraethylorthosilicate concentration (C-TE(OS)), ammonia hydroxide concentration (C-NH3(center dot H2O) ) and dichloromethane content on the size and morphology of the SSNs were investigated. The average diameters of the SSNs increased with increasing C-TEOS and C-NH3 center dot H2O. However, the effect of increasing C-NH3 center dot H2O on the particle size is more significant. The time evolution of the morphology and diameter of the SSNs were also investigated to elucidate the growth mechanism for the SSNs synthesized in the O/W SFMEs. (C) 2018 Elsevier Inc. All rights reserved.