DFT-based electronic structure calculations are performed on a series of compounds designed to model the hydrogen bonding present in sulfonic acid-doped polyaniline. A thorough investigation of the structural and electronic influences on the hydrogen bonding at the B3LYP/6-311++G(2d,2p) level reveals a number of previously unknown features of such systems. Rearrangements of both the geometry and electronic configuration indicate that the creation of a hydrogen bond between the N-H group in the polyaniline models and the O-S group in the sulfonic acid models increases the ability of the phenyl-nitrogen backbone to transfer electron density.