In this study, the formation of silica–chitosan hybrid materials via sol–gel process under pH values of 2–6 were investigated using N2 sorption analysis, scanning electron microscopy, transmission electron microscopy, thermal analysis and zeta potential analyzer. The hierarchical structure consisting of meso- and macropore was formed when pH value was higher than 2. Mesopores were formed as the interparticle channels of silica nanoparticles aggregates, whereas macropores were the void between the aggregates (clusters). The clusters size was decreased with increasing the pH value, resulting in the increase of the macroporosity. The thermal conductivity of the products was controlled in the range of 0.06 and 0.13 W m−1 K−1 by varying the product porosity between 88 and 69% (pH 6 and pH 2, respectively).