MXenes　have　been　considered　as　promising　electrode　materials　for　capacitive　deionization　(CDI).　However,　the　availability　of　space　for　trapping　and　storing　ions　is　usually　inhibited　in　Mxene-based　assemblies　due　to　their　special　lamellar　structure,　which　affects　their　desalination　performance.　Herein,　a　kind　of　N-doped　Ti3C2Tx　electrode　with　a　unique　interconnected　porous　structure　(N-3DM-S)　is　designed　to　improve　the　active　site　accessibility　of　the　electrodes.　The　Ti3C2Tx　shell　layers　with　flaws　are　prepared　on　spherical　sacrificial　templates,　which　then　lead　to　the　formation　of　an　interconnected　N-doped　porous　architecture　upon　the　heat　treatment　under　an　NH3　atmosphere.　The　interconnected　porous　feature　improves　the　availability　of　electrode　materials,　while　the　doping　of　nitrogen　further　enhances　the　accessibility　of　the　electrode　to　electrolyte　in　addition　to　the　chemical　and　electrochemical　properties.　As　a　result,　the　as-obtained　N-3DM-S　samples　with　more　valid　surface　active　sites　exhibit　excellent　CDI　performance　compared　to　the　control　samples　with　isolated　pore　structure　and　the　ones　without　N-doping.　In　particular,　the　optimal　CDI　capacities　of　N-3DM-S　electrodes　can　reach　up　to　53　±　2　mg　g-1　in　aqueous　NaCl　of　5000　mg　L-1　at　1.6　V.　Moreover,　such　N-3DM-S　electrodes　exhibit　good　regeneration　stability　as　well,　indicating　their　potential　applications　in　the　field　of　desalination.　©　2022　The　Royal　Society　of　Chemistry.