A method of preparing 5-methylresorcinol and formaldehyde based organic aerogels in non-aqueous media with a benzoic acid derivative as a catalyst is being proposed in this paper. Here acetonitrile is used as a solvent that allows direct drying with carbon dioxide over the supercritical state without the need for a solvent exchange. The acidic properties of 2,6-dihydroxy-4-methyl benzoic acid promote the reaction of sol–gel polymerization, and at the same time it takes part in the reaction as a co-monomer and influences the nanostructure of the material. The evolution of the polymer was monitored using nuclear magnetic resonance spectroscopy and the structure of the resulting organic aerogels depending on the molar ratio of 5-methylresorcinol to 2,6-dihydroxy-4-methyl benzoic acid was studied by nitrogen adsorption–desorption measurements, scanning electron microscopy and infrared spectrometry.