Self‐assembling building blocks like the 4‐pyridone can exhibit extraordinary H‐bond‐aromaticity coupling effects. Computed dissected nucleus independent chemical shifts (NICS(1)zz), natural bond orbital (NBO) charges, and energy decomposition analyses (EDA) for a series of hydrogen (H‐) bonded 4‐pyridone chains (4‐py)n (n = 2 to 8) reveal that H‐bonding interactions can polarize the 4‐pyridone exocyclic C=O bonds and increase 4n+2 π‐electron delocalization in the six‐membered ring. The resulting H‐bonded 4‐pyridone units display enhanced π‐aromatic character (both magnetically and energetically) and their corresponding NH···OC interactions are strengthened. These π‐electron polarization effects do not depend on the relative orientations (co‐planar or perpendicular) of the neighboring 4‐pyridone units, but increase with the number of H‐bonded units. © 2015 Wiley Periodicals, Inc.