The　superior　capability　of　gemini　surfactant　(GS)　in　the　preparation　of　hierarchically　porous　carbons　via　high-internal-phase　emulsion　(HIPE)　template　followed　by　pyrolysis　was　confirmed　in　this　work.　Polymerized　HIPEs　(polyHIPEs)　of　phenol-formaldehyde　resin　were　prepared　by　cross-linking　the　continuous　phase　of　HIPEs　stabilized　by　GS.　Nonionic　surfactant　and　cationic　surfactant　were　also　selected　to　stabilize　HIPE　for　comparison.　From　scanning　electron　microscope　observations,　polyHIPEs　with　open-cell　pore　architectures　were　obtained　with　GS　as　emulsifier　(polyHIPEs-GS)　and　the　derived　carbon　foams　(carboHIPEs-GS)　well　retained　the　original　pore　architectures,　whereas　polyHIPEs　obtained　using　contrastive　surfactants　showed　closed-cell　porous　structures　and　notable　differences　were　observed　for　the　derived　carboHIPEs.　Nitrogen　adsorption/desorption　measurements　indicated　that　polyHIPEs-GS　and　carboHIPEs-GS　both　exhibited　hierarchically　porous　architectures　with　much　higher　surface　areas　(SA)　than　those　of　the　corresponding　contrast　samples.　Mercury　intrusion　porosimetry　results　indicated　that　carboHIPEs-GS　possessed　higher　SA　and　higher　porosity　than　that　of　the　contrast　samples.　The　open-cell　pore　architecture　and　high　SA　are　favorable　to　many　applications,　like　energy　storage.　carboHIPE-GS　expectably　showed　a　higher　capacitance　than　that　of　contrast　samples　when　used　as　the　electrode　material　of　supercapacitor.　©　2018　American　Chemical　Society.