The dielectric relaxation of polar stickers capable of binary hydrogen bond complexation is studied theoretically and compared to experiment. In the model system, free and complexed units are considered in equilibrium. The theoretical evaluation shows that the dipole correlation function of complexes cannot be described by a simple exponential decay, as is usually assumed in dielectric spectroscopy. Complex reorientation and dissociation contribute simultaneously to the dielectric relaxation. The theoretical results are compared to experimental data obtained on polybutadiene which is functionalized at low concentration (x = 0.02, 0.03, and 0.04) by 4-phenyl-1,2,4-triazoline-3,5-dione (4-phenylurazole (PU)) units. From the comparison of recent dielectric and dynamic mechanical measurements, the relaxation times of the reorientation of dimeric complexes are calculated and compared with the lifetime of dimeric contacts. From the relaxation strength of the relaxation of complexed urazoles, the dipole moment is calculated and compared with the result of a force field calculation. Both methods reveal a slightly twisted structure of the dimeric complexes.