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The effect of glycerol (GLY) and poly(ethylene glycol) (PEG) additives on the properties of silica aerogel-like monoliths obtained from methyltrimethoxysilane (MTMS) precursor was assessed. The tested molar ratios of additive/precursor were from 0 to 0.1 and the lowest bulk densities were obtained with a ratio of 0.025. When a washing step was performed in the sample containing the optimum PEG ratio, the bulk density could be reduced even further. The analysis of the material’s microstructure allowed us to conclude that GLY, if added in an optimum amount, originates a narrower pore size distribution with a higher volume of mesopores and specific surface area. The PEG additive played a binder effect, leading to the filling of micropores and the appearance of large pores (macropores), which caused a reduction in the specific surface area. The reduction of the bulk density and the microstructural changes in the aerogels induced by adding a small amount of these additives confirm the possibility of fine control of properties of these lightweight materials. The achieved high porosity (97%) and low thermal conductivity (~35 mW·m^−1·K^−1) makes them suitable to be used as thermal insulators.