The precise spatial positioning of functional groups in biomacromolecules leads to astonishing binding, catalytic, and transport capabilities. In contrast, synthetic frameworks capable of convergently locking functional groups with minimized conformational uncertainty are highly desirable but rare. Here we report C5-symmetric aromatic pentaamide macrocycles c5a-c synthesized in one pot from the corresponding monomers. The crystal structure of c5c reveals a fully constrained backbone that enforces ten alternating NH/CH hydrogen-bond donors and five large amide dipoles to point to the center of the macrocycle. With a highly electropositive cavity in a high-energy unbound state, macrocycles c5 bind anions in a 1:1 stoichiometry in solution, with Ka values up to 106 M-1 for halides and 108 M-1 for oxoanions. Macrocycle c5a was able to selectively transport chloride ions across lipid bilayers. The extraordinary binding of phosphate-related ions by c5 also enabled catalytic ester amidation owing to the stabilization of the corresponding transition states.