The　development　of　polymer　composite　dielectrics　exhibiting　high　dielectric　constant,　low　dielectric　loss,　and　excellent　environmental　stability　is　essential　for　enhancing　field-effect　transistor　(FET)　performance　and　reliability.　While　conventional　high-kappa　materials　like　Al2O3　suffer　from　surface　hydrolysis-induced　polarization　inhomogeneity,　we　present　herein　a　molecular　engineering　solution　through　solution-processable　and　structurally　programmable　Al8　macrocycles.　By　employing　computationally　guided　metal　center　and　macrocycle　surface　engineering,　we　achieved　highly　efficient　synthesis　of　solution-processable　Al8-based　dielectric　materials.　The　resulting　series　of　10　structurally　programmed　Al8　macrocycles　creates　tailored　electronic　microenvironments,　delivering　exceptional　dielectric　properties:　a　threefold　enhancement　in　dielectric　constant　compared　to　pure　polymer　matrices,　remarkably　low　dielectric　loss　(tan　delta　=　0.064),　and　superior　humidity　resistance　versus　conventional　Al2O3　fillers.　This　work　establishes　a　comprehensive　materials　paradigm　that　simultaneously　optimizes　the　critical　dielectric　parameters　(kappa,　tan　delta,　and　moisture　resistance)　while　demonstrating　the　versatility　of　cluster　molecular　design.