Multicomponent organic crystals built from acid−base complexes which possess biological activity are a forthcoming trend in modern chemistry. They play an important role in the development of predictable assembly of supramolecular architectures and control of polymorphism. This study is focused on the design, synthesis and structure investigation of new compounds based on biologically active components: different alkanolamines as cations and 4-nitrobenzoic acid as anion, as active ingredients in the medical-pharmaceutic field. Besides their significant biological activities, both alkanolamines and 4-nitrobenzoic acid have the ability to form strong and directional hydrogen bonds resulting in supramolecular systems with different topologies. Herein, we present the single crystal X-ray analysis of six ionic crystals which comprise 4-nitrobenzoic acid and ethanolamine, methylethanolamine, ethylethanolamine, diethanolamine and triethanolamine. The analysis of supramolecular architecture of ionic crystals has revealed that in all samples with 1:1 stoichiometry the 4-nitrobenzoic acid is deprotonated and alkanolamines are protonated and number of hydrogen atoms on amine nitrogen dramatically influence on hydrogen pattern. In the case of alkanolamines with primary and secondary nitrogen atom, the amine group of cation and carboxylic group of anion form invariably N–H ···O and O–H···O hydrogen bonds (Figures 1a and 1b). Thus, such interactions represent the reliable supramolecular synthon. In the case of triethanolamine the only one hydrogen atom on amine nitrogen participate in the formation of H-bonded centrosymmetric dimer through two N-H···O hydrogen bonds. The 4-nitrobenzoate anion forms only O–H···O H-bonds with triethanolamine, Figure 1c. (a) (b) (c)