Crystal structures of seven salts of 2-hydroxyethylamine with benzoic acid (1) and different substituted benzoic acids, such as p-methylbenzoic acid (2), p-methoxybenzoic acid (3), p-hydroxybenzoic acid (4), p-chlorobenzoic acid (5), p-bromobenzoic (6), and p-iodobenzoic (7) have been studied. The salts units of 1−7 serve as building blocks (BB) of the supramolecular architecture. In a crystal they are held together via proton-transferred N−H•••O and normal O− H•••O hydrogen bonds. The substituents on anions influence dipole−dipole interactions between anions and cations in molecular aggregates. As a result, they are organized in building blocks either via one charge-assisted (1, 2) hydrogen bond or via two (3−7) hydrogen bonds. The dispersion interaction significantly contributes to intermolecular force fields driving the organization of hydrogen bonds in BB. In all studied compounds, building blocks are consolidated into 2-D layers through the N−H•••O and O−H•••O hydrogen bonds.For the crystal structures of 2−7, with non-centrosymmetric space groups and the BB self-assembled by two hydrogen bonds, the macroscopic polarizations of a unit cell is practically perpendicular to the layers.