Polyamide　(PA)　nanofiltration　membranes　have　raised　considerable　interest　in　the　realm　of　water　purification.　However,　balancing　permeability　and　rejection　remains　a　critical　challenge　in　membrane　science　and　technology.　Herein,　we　report　that　weak　non-covalent　hydrogen　bonds　and　strong　coordination　bonds　between　ultrathin　calcium　silicate　(UCS)　interlayers　and　piperazine　(PIP)　powerfully　control　its　diffusion.　Theoretical　calculations　reveal　that　coordination　bonds　dominate　PIP　binding　on　UCS　with　an　adsorption　energy　of　−443.83　​kJ　​mol−1,　thereby　impeding　its　movement.　The　diffusion　coefficient　of　PIP　diminishes　by　14　​%　upon　the　incorporation　of　UCS,　as　evidenced　by　molecular　dynamics　simulations.　As　a　consequence,　a　superhydrophilic,　smooth,　loose,　and　ultrathin　(∼18.9　​nm)　PA　separation　layer　is　created.　The　as-obtained　UCS-interlayered　PA　possesses　a　remarkable　water　permeance　of　31.7　​L　​m−2　​h−1　​bar−1　that　is　2.2-fold　higher　than　that　of　UCS-free　PA,　while　dye　rejection　rates　keep　a　high　level.　Furthermore,　the　UCS-interlayered　PA　demonstrates　exceptional　antifouling　performance　with　a　95　​%　flux　recovery　ratio　and　long-term　stability　during　16-h　filtration.　The　study　highlights　the　pivotal　role　of　mineral　interlayers　in　tailoring　amine　monomer　diffusion　via　multiple　interfacial　interactions　for　advanced　water　treatment　applications.　©　2025　The　Authors