A new flexible hydrogen‐bonded supramolecular host based on two deoxypyridinoline‐bioinspired 6‐hexanoic acid‐substituted 3‐hydroxypyridinium cations that adopt the twist and planar conformations and construct the orthogonal single helical scaffold and sheet structures with the triangular NO3− and spherical Br− guest anions, respectively. The results demonstrated not only the importance of rotational flexibility, anion shapes, and robust C—H⋯O hydrogen bonding, but also the good antibacterial activity with the potential antibacterial application. [ABSTRACT FROM AUTHOR]