Provided is a gelled carbon-based composition forming an organic polymeric monolithic gel capable of forming a porous carbon monolith by pyrolysis, a use thereof and a process for preparing this composition. A composition according to the invention is based on a resin derived at least partly from polyhydroxybenzene(s) R and formaldehyde(s) F, has a thermal conductivity of less than or equal to 40 mW·m−1·K−1, and includes at least one water-soluble cationic polyelectrolyte P. A process for preparing this composition comprises: a) polymerization, in an aqueous solvent, of the polyhydroxybenzene(s) and formaldehyde(s), in the presence of at least one cationic polyelectrolyte dissolved in this solvent and of a catalyst, in order to obtain a solution based on the resin, b) gelling of the solution in order to obtain a gel, and c) drying in order to obtain the organic polymeric monolithic gel.