The dynamics and thermodynamics of the Debye and structural (α) relaxations in isomeric monoalcohols near the glass transition temperature Tg are explored using dielectric and calorimetric techniques. The α relaxation strength at Tg is found to correlate with the heat capacity increment, but no thermal signals can be detected to link to the Debye relaxation. We also observed that the activation energy of the Debye relaxation in monoalcohols is quantitatively correlated with that of the α relaxation at the kinetic Tg, sharing the dynamic behavior of the Rouse modes found in polymers. The experimental results together with the analogy to the Rouse modes in polymers suggest that the Debye process in monoalcohols is an entropic process manifested by the total dipole fluctuation of the supramolecular structures, which is triggered and driven by the α relaxation.