A novel method of microemulsion coupling with sol–gel process was used for preparation of porous silica using tetraethyl orthosilicate as silicon source. Effect of solvent and catalyst on the surface texture properties was investigated respectively. The results showed that porous silica with large specific surface area (738.65 m2/g) and high pore volume (2.01 cm3/g) was obtained. However, the mesopores in silica were arranged in disorder and showed great ununiformity in shape and arrangement. To obtain porous silica with desired texture properties, an appropriate dosage of ethanol and higher HCl concentration were needed.