The success of the emerging field of solid-state optical quantum information processing (QIP) critically depends on the access to resonant optical materials. Rare-earth ion (REI)-based molecular systems, whose quantum properties could be tuned taking advantage of molecular engineering strategies, are one of the systems actively pursued for the implementation of QIP schemes. Herein, we demonstrate the efficient polarization of ground-state nuclear spins-a fundamental requirement for all-optical spin initialization and addressing-in a binuclear Eu(III) complex, featuring inhomogeneously broadened D  → F optical transition. At 1.4 K, long-lived spectral holes have been burnt in the transition: homogeneous linewidth (Γ ) = 22 ± 1 MHz, which translates as optical coherence lifetime (T ) = 14.5 ± 0.7 ns, and ground-state spin population lifetime (T ) = 1.6 ± 0.4 s have been obtained. The results presented in this study could be a progressive step towards the realization of molecule-based coherent light-spin QIP interfaces.