AbstractThe synthesis of several calix[4]arenes functionalized with uracil or diaminotriazine moieties is described. The association between these complementary calix[4]arenes is strongly influenced by processes related to the position and directionality of the hydrogen‐bonding moieties. In the case of bis(uracil)calix[4]arene (4), self‐association is observed (K= 3.4 · 103M−1in CDCl3) whereas, in the case of bis(diamidotriazine)calix[4]arene (16), it was concluded from1H‐NMR studies that intermolecular association is hampered by the formation of intramolecular hydrogen bonds. Due to the divergent orientation of the hydrogen‐bonding groups of bis(diaminotriazine)calix[4]arene (15b), it forms hydrogen‐bonded strands through interaction with 5‐ethyl‐5‐phenylbarbituric acid (17), resulting in the formation of a