The recognition of self-complementary quadruple urea aminotriazine (UAT)-based hydrogen-bonded arrays was investigated in solution and at surfaces. For this purpose, an UAT-based donor-acceptor-donor-acceptor (DADA) array and complementary receptors were synthesized. Two-dimensional proton nuclear magnetic resonance ((1)H NMR) measurements in CDCl(3) pointed at an intramolecular hydrogen-bond stabilization of the UAT, which promotes a planar molecular geometry and, thereby, results in a significant stabilization of the dimeric complex. The bond strength of the UAT dimers at surfaces was determined by atomic force microscopy-based single molecule force spectroscopy (AFM-SMFS) in hexadecane. The UAT receptor was immobilized on gold surfaces using an ultrathin layer of ethylene glycol terminated lipoic acid and isocyanate chemistry. The layers obtained and the reversible self-complementary recognition were thoroughly characterized with contact angle measurements, grazing angle Fourier transform infrared (FTIR) spectroscopy, X-ray photoelectron spectroscopy (XPS), and AFM. Loading rate-dependent SMFS measurements yielded a barrier width x(beta) and a bond lifetime at zero force t(off)(0) of 0.29 +/- 0.02 nm and 100 +/- 80 ms, respectively. The value of the corresponding off-rate constant k(off) suggests a substantially larger value of the dimerization constant compared to theoretical predictions, which is fully in line with the additional intramolecular hydrogen-bond stabilization detected in solution by (1)H NMR spectroscopy.