The fluorination of porous materials often leads to the enhancement of properties such as stability, crystallinity and selective adsorption. Although there has been much interest in the fluorination of many types of porous materials, little research has been done on the fluorination of macrocycles, specifically trianglimine and leaning pillararene based materials. In this work, we introduce for the first time highly fluorinated trianglimine and leaning pillararene and show the enhancement effects brought about by the inclusion of fluorinated-phenyl moieties, such as increased stability, surface area, and tendency for self-assembly in our systems. We then show how our fluorinated macrocycles open the door for the formation of extended macrocycle-based polymetric materials simply and in high yields via nucleophilic aromatic substitution. We show for the first time the formation of a trianglimine-based cross-linked polymer and demonstrate its use for micropollutant and gas separation.