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(polyHlPEs-GS)　and　the　derived　carbon　foams　(carboHlPEs-GS)　well　retained　the　original　pore　architectures,　whereas　polyHlPEs　obtained　using　contrastive　surfactants　showed　closed-cell　porous　structures　and　notable　differences　were　observed　for　the　derived　carboHlPEs.　Nitrogen　adsorption/desorption　measurements　indicated　that　polyHlPEs-GS　and　carboHlPEs-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　7　carboHlPEs-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.　carboHlPE-GS　expectably　showed　a　higher　capacitance　than　that　of　contrast　samples　when　used　as　the　electrode　material　of　supercapacitor.