Association of four N-(pyridin-2-yl),N'-R(1)-ureas (R(1) = ethyl, n-butyl, phenyl, and tert-butyl) with substituted 2-amino-1,8-naphthyridines and benzoates were studied by (1)H NMR spectroscopic titrations and quantum chemical calculations. The benzoates and 2-amino-1,8-naphthyridines were selected as representatives of double and triple hydrogen bonding counterparts, respectively. The classical substituent effect on the association was studied. A prerequisite and a crucial step for the complex formation was the breaking of the intramolecular hydrogen bond in urea derivatives. The QTAIM calculation method was employed to explain the hydrogen bonding within complexes. In the case of benzoates carrying an electron-donating substituent the experimental findings were explained by the formation of two complexes. These observations were rationalized by the electronic repulsions between atoms in a close proximity and further verified by calculations. Single-crystal X-ray diffraction was used to confirm the structure of studied ureas in the crystalline state. These results are in line with the solution studies of self-association of ureas.