The small upper Pleistocene diatreme of Polino (central Italy) is known in literature as one of the few monticellite alvikites (volcanic Ca-carbonatite) worldwide. This outcrop belongs to the Umbria-Latium Ultra-alkaline District (ULUD), an area characterized by scattered and small-volume strongly SiO2-undersaturated ultrabasic igneous rocks located in the axial sector of the Apennine Mts. in central Italy. Petrographic and mineralogical evidences indicate that Polino olivine and phlogopite are liquidus phases rather than mantle xenocrysts as instead reported in literature. The presence of monticellite as rim of olivine phenocrysts and as groundmass phase indicates its late appearance in magma chambers at shallow depths, as demonstrated by experimental studies too. The absence of plagioclase and clinopyroxene along with the extremely MgO-rich composition of olivine (Fo92–94) and phlogopite (average Mg# ~93) suggest for Polino magmas an origin from a carbonated H2O-bearing mantle source at depths at least of 90–100 km, in the magnesite stability field. In contrast with what reported in literature, the ultimate strongly ultrabasic Ca-rich whole-rock composition (~15–25 wt% SiO2, ~31–40 wt% CaO) and the abundant modal groundmass calcite are not pristine features of Polino magma. We propose that the observed mineral assemblage and whole-rock compositions result mostly from the assimilation of limestones by an ultrabasic melt at a depth of ~5 km. A reaction involving liquidus olivine + limestone producing monticellite + CO2 vapour + calcite is at the base of the origin of the Polino pseudocarbonatitic igneous rocks.