Understanding quantum thermalization through entanglement build up in isolated quantum systems addresses fundamental questions on how unitary dynamics connects to statistical physics. Spin systems made of long-range interacting atoms offer an ideal experimental platform to investigate this question. Here, we study the spin dynamics and approach towards local thermal equilibrium of a macroscopic ensemble of S = 3 chromium atoms pinned in a three dimensional optical lattice and prepared in a pure coherent spin state, under the effect of magnetic dipole–dipole interactions. Our isolated system thermalizes under its own dynamics, reaching a steady state consistent with a thermal ensemble with a temperature dictated from the system’s energy. The build up of quantum correlations during the dynamics is supported by comparison with an improved numerical quantum phase-space method. Our observations are consistent with a scenario of quantum thermalization linked to the growth of entanglement entropy.