Capacitive　deionization　(CDI)　represents　one　of　the　most　thermodynamically　efficient　technologies　for　brackish　water　desalination.　Its　performance　is　highly　reliant　on　the　surface　properties　of　carbon-based　electrodes.　Zeolitic-imidazolate　framework　(ZIF)-derived　carbon　materials　have　emerged　among　the　most　promising　candidates　owing　to　their　high　structural　and　compositional　tuneability.　However,　the　impacts　of　the　precursory　ZIF　structure　on　the　properties　of　the　final　carbon,　and　therefore,　CDI　capacity　and　efficiency　remain　to　be　further　explored.　In　this　work,　four　Zn-based　ZIFs　with　different　side-chain　substitutions　on　the　imidazolates　were　synthesized　on　a　gram　scale　with　high　yields　to　produce　N-doped　carbons　by　pyrolysis.　The　resulting　carbons　along　with　four　commercial　carbon　blacks　were　characterized　physically　and　electrochemically　to　explore　the　structure-performance　relationship.　We　demonstrated　that　the　imidazole　side-chain　substitution　alters　the　ZIF＇s　decomposition　during　pyrolysis,　influencing　the　elemental　compositions,　surface　properties,　wettability　and　graphitization　levels.　The　diverse　carbon　properties　result　in　variable　double　layer　capacitance　and　charge-transfer　resistance,　ultimately　impacting　the　CDI　performance.　Among　these　carbons,　Zn　(4abIm)(2)-C　afforded　the　greatest　salt　adsorption　capacity　of　14.19　mgNacl.g(C)(-l),　while　Zn　(mlm)(2)-C　showed　the　highest　overall　salt　adsorption　capacity　and　rate;　both　exceeded　the　performance　of　the　commercial　carbon　blacks.