We investigate the mechanism of spin-lattice relaxation of Er ions encapsulated in polyoxometalate clusters, which below 4 K can only reverse its spin via quantum tunneling processes. The temperature-independent rate −1 is, at zero field, ten orders of magnitude larger than the rates predicted for direct phonon-induced processes. In addition, we observe that −1 is suppressed by external magnetic bias and hyperfine interactions but enhanced by increasing the concentration of Er ions. The observed relaxation agrees with predictions for pure quantum tunneling, showing that this phenomenon drives the thermalization of electronic spins. A possible link between these two phenomena is discussed, involving the collective emission of phonons from particular spin configurations attained via quantum tunneling. The fundamental equations of magnetism, including Curie's law, rely on the ability of magnetic moments to attain thermal equilibrium with the solid lattice. In spite of the progress achieved in studying and manipulating individual spins in solids, 1 the spin-lattice relaxation ͑SLR͒ mechanisms are not well understood yet. An intriguing situation arises, near zero field, for strongly anisotropic spins, e.g., magnetic molecular clusters or rare-earth ions. When thermally activated tunneling processes 2 die out, at sufficiently low temperatures ͑typically T Շ 1 K͒, spins can only flip by pure quantum tunneling ͑QT͒ across the anisotropy energy barrier. Theoretical descriptions 3-5 of QT in the presence of hyperfine couplings and dipolar spin-spin interactions account well for experiments that measure the time-dependent magnetization under such conditions. 6-8 Concerning SLR, a major difficulty arises. It stems from the fact that QT modifies the magnetization but conserves the energy of the ensemble of nuclear and electronic spins. Therefore, equilibrium states might well be reached long after the characteristic time scales of QT. However, a few experiments suggest otherwise. Specificheat studies 10 indicate that Mn 4 and Fe 8 single-molecule magnets ͑SMM͒ attain thermal equilibrium at rates comparable to those found in magnetization relaxation experiments. In addition, NMR experiments on Mn 12 clusters 11 show that the nuclear spin and bath temperatures remain the same down to the neighborhood of absolute zero.In order to elucidate the nature of the SLR mechanism and its relationship with QT, direct measurements of the SLR rates as a function of temperature, magnetic field, concentration of spins, etc., are clearly desirable. Studying the SLR of molecular nanomagnets at very low temperatures and under weak magnetic fields is, however, a demanding experimental task because tunneling time scales are on the order of days even for clusters made of a few atoms. In order to overcome this difficulty, simpler molecules need to be studied. In the present work, we report the SLR rates of polyoxometalate ͑POM͒ clusters containing individual lanthanide ions. The results evidence that the thermalization of electronic spins is dictat...