Calcioolivine has been included into the MDI mineral database in the list of grandfathered minerals. Its history, together with related artificial compounds, is extremely complex: various minerals and compounds received this name, including natural orthorhombic Ca orthosilicate. In this paper, the crystal structure and properties of natural calcioolivine are described for the first time. The new mineral has been found at Mt. Lakargi, Upper Chegem Plateau, the northern Caucasus, Kabarda-Balkaria Republic, Russia. It has been identified in skarnified, primary carbonate xenoliths entrained by middle to late Pliocene silicic ignimbrites of the Upper Chegem caldera. These xenoliths of a few centimeters to a few meters in size are located close to the volcanic vent. Calcioolivine rims relics of larnite and occurs as relict grains among crystals of spurrite, rondorfite, wadalite or secondary hillebrandite, afwillite, thaumasite, and ettringite. Hillebrandite is the major product of alteration of calcioolivine; larnite is relatively more resistant to low-temperature alteration. Spurrite, larnite, tilleyite, kilchoanite, cuspidine, wadalite, rondorfite, reinhardbraunsite, lakargiite (CaZrO₃), members of ellestadite series, afwillite, ettringite, katoite, and thaumasite are associated minerals. It is inferred that calcioolivine has been produced as a result of interaction of host carbonate rocks in xenoliths with volcanic lava and gases during eruption. The name calcioolivine was approved by the Commission on New Minerals and Mineral Names, International Mineralogical Association, September 6, 2007 (no. 07-B).