Carboxylic acid-acid hydrogen-bonding dimer and acid-pyridine hydrogen-bonding motif are two competing supramolecular synthons that a molecule possessing both carboxylic acid and pyridine functional groups could form in the solid state. Their coexistence has been observed but for the molecules with the molar ratio of carboxylic acid and pyridine groups being greater than 1:1. In this crystal engineering study, 2-[phenyl(propyl)amino]nicotinic acid with a 1:1 molar ratio of these two functional groups was discovered to have two polymorphs, in which one consists of unique hydrogen-bonded tetramer units bearing both acid-acid and acid-pyridine hydrogen-bonding motifs, while the other is composed of acid-pyridine hydrogen-bonded chains. Quantum mechanical calculations were employed to unravel the essence of the coexistence of the two vying counterparts as well as the origins of the tetramer and chain structures.