A series of relativistic prolapse-free Gaussian basis sets of quadruple-ζ quality has been developed: (aug-)RPF-4Z. Here, we report the (aug-)RPF-4Z sets for all the d-block elements (Sc-Cn). Molecular calculations at the Coupled Cluster level showed a significant reduction in computational demand in comparison with other well-known relativistic quadruple-ζ sets. The (aug-)RPF-4Z sets in a ready-to-use format are available as Supporting Information and can also be found at http://basis-sets.iqsc.usp.br/.