Methods of forming a hierarchical porous monolith are provided. The methods include mixing a monomer, a silica precursor and a catalyst in a solvent to form a mixture. The methods also include adding a gelling agent to the mixture to form a polymer-silica composite gel. The polymer-silica composite gel undergoes a phase separation to separate from the solvent and the unreacted silica precursor. The method further includes drying the polymer-silica composite gel to evaporate the solvent to form a polymer-silica monolith and processing the polymer-silica monolith to form at least one of a polymer monolith, a carbon monolith, a silica monolith and a carbon-silica monolith.