Mantle xenoliths sampled by kimberlite and alkali basalt magmas show a range of metasomatic styles, but direct evidence for the nature of the metasomatising fluids is often elusive. It has been suggested that carbonate-rich melts produced by partial melting of carbonated peridotites and eclogites play an important role in modifying the composition of the lithospheric mantle. These mantle-derived carbonate melts are often inferred to be enriched in alkali elements; however, alkali-rich carbonate fluids have only been reported as micro-inclusions in diamonds and as unique melts involved in the formation of the Udachnaya-East kimberlite (Yakutia, Russia). In this paper we present the first direct evidence for alkali-carbonate melts in the shallow lithospheric mantle (∼110–115 km), above the diamond stability field. These alkali-carbonate melts are preserved in primary multiphase inclusions hosted by large metasomatic ilmenite grains contained in a polymict mantle xenolith from the Bultfontein kimberlite (Kimberley, South Africa). The inclusions host abundant carbonates (magnesite, dolomite, and K-Na-Ca carbonates), kalsilite, phlogopite, K-Na titanates, and phosphates, with lesser amounts of olivine, chlorides, and alkali sulfates. Textural and chemical observations indicate that the alkali-carbonate melt likely derived from primary or precursor kimberlite magmas. Our findings extend the evidence for alkali-carbonate melts/fluids permeating the Earth mantle outside the diamond stability field and provide new insights into the chemical features of previously hypothesized melts. As metasomatism by alkali-rich carbonate melts is often reported to affect mantle xenoliths, and predicted from experimental studies, the fluid type documented here likely represent a major metasomatising agent in the Earth’s lithospheric mantle.