The extreme depletion of the Earth’s mantle in sulfur is commonly seen as a signature of metal segregation from Earth’s mantle to Earth’s core. However, in addition to S, the mantle contains other elements as volatile as S that are hardly depleted relative to the lithophile volatility trend although they are potentially as siderophile as sulfur. We report experiments in metal-sulfide–silicate systems to show that the CI normalized abundances of S, Pb, and Sn in Earth’s mantle cannot be reproduced by element partitioning in Fe ± S–silicate systems, neither at low nor at high pressure. Much of the volatile inventory of the Earth’s mantle must have been added late in the accretion history, when metal melt segregation to the core had become largely inactive. The great depletion in S is attributed to the selective segregation of a late sulfide matte from an oxidized and largely crystalline mantle. Apparently, the volatile abundances of Earth’s mantle are not in redox equilibrium with Earth’s core.