The influence of acetic acid on the pore structure and surface area of silica prepared by the sol-gel method was investigated. Experimental conditions of synthesis, such as gelation temperature and solvents, were also studied. N2 adsorption isotherms of the samples were type 1, typical of microporous materials, explaining the high surface area values (BET) observed. The simultaneous addition of acetic and hydrochloric acids as catalysts and of acetone as solvent, together with the use of a gelation temperature of 20 °C, made it possible to prepare amorphous silica materials with surface area values up to 850 m2 g-1. The high surface area value of these samples could be explained by the microporosity and the nanometric size of the particles. ©2007 Sociedade Brasileira de Química.