Freestanding　electrodes　without　the　influences　of　additives　have　been　considered　as　a　kind　of　ideal　electrode　structure　in　the　field　of　capacitive　deionization　(CDI).　However,　subjected　to　conductivity,　available　surface　areas,　hydrophilicity　and　etc.,　effectively　construction　of　freestanding　CDI　electrodes　with　high　water　desalination　performance　still　face　great　challenges.　Herein,　we　will　demonstrate　a　unique　N-doped　graphene　freestanding　porous　membrane　electrode　with　excellent　water　desalination　performance.　The　preparation　process　mainly　includes　the　assembly　of　core-shell　composites　with　incomplete　graphene　oxide　shells　into　bulk　membranes　using　compression　molding　method　and　the　heat-treatment　under　NH3　atmosphere.　These　reserved　spherical　shells　with　loopholes　and　N-doping　make　up　the　freestanding　membrane　electrodes　with　network　porous　architecture.　The　interconnected　sphere　shells　efficiently　improve　the　availability　of　surface　and　pores　in　the　monolithic　assembly,　while　the　doping　of　nitrogen　element　further　enhances　the　accessibility　of　graphene-based　surface　by　the　electrolyte.　As　a　result,　such　graphene　carbonaceous　freestanding　electrodes　exhibit　excellent　water　desalination　performance　with　a　high　CDI　capacity　of　about　21.8　mg/g　in　NaCI　solution.　Moreover,　such　freestanding　membrane　electrodes　also　possess　good　desalination　abilities　towards　some　other　salts　such　as　KCI,　CaCl2　and　MgCl2,　suggesting　their　potential　applications　in　complex　brine　solution.　(C)　2021　Elsevier　Ltd.　All　rights　reserved.