Monticellite is a magmatic and/or deuteric mineral that is often present, but widely varying in concentrations in Group-I (or archetypal) kimberlites. To provide new constraints on the petrogenesis of monticellite and its potential significance to kimberlite melt evolution, we examine the petrography and geochemistry of the minimally altered hypabyssal monticellite-rich Leslie (Canada) and Pipe 1 (Finland) kimberlites. In these kimberlites, monticellite (Mtc) is abundant (25–45vol%) and can be classified into two distinct morphological types: discrete and intergrown groundmass grains (Mtc-I), and replacement of olivine (Mtc-II).Primary multiphase melt inclusions in monticellite, perovskite and Mg-magnetite contain assemblages dominated by alkali (Na, K, Ba, Sr)-enriched Ca-Mg-carbonates, chlorides, phosphates, spinel, silicates (e.g. olivine, phlogopite) and sulphides. These melt inclusions probably represent snapshots of a variably differentiated kimberlite melt that evolved in-situ towards carbonatitic and silica-poor compositions. Although unconstrained in their concentration, the presence of alkali-carbonates and chlorides in melt inclusions suggests they are a more significant component of the kimberlite melt than commonly recorded by whole-rock analyses.We present petrographic and textural evidence showing that pseudomorphic Mtc-II resulted from an in-situ reaction between olivine and the carbonate component of the kimberlite melt in the decarbonation reaction:Forsterite+Carbonatemelt⇌Monticellite+Periclase+CO2.This reaction is supported by the preservation of abundant primary inclusions of periclase and to a lesser extent Fe-Mg-oxides in monticellite, perovskite and Mg-magnetite. Based on the preservation of primary periclase inclusions, we infer that periclase also existed in the groundmass, but was subsequently altered to brucite.We suggest that CO2 degassing in the latter stages of kimberlite emplacement into the crust is largely driven by the observed reaction between olivine and the carbonate melt. For this reaction to proceed, CO2 should be removed (i.e. degassed), which will cause further reaction and additional degassing in response to this chemical system change (Le Chatelier's principle). Our study demonstrates that these proposed decarbonation reactions may be a commonly overlooked process in the crystallisation of monticellite and exsolution of CO2, which may in turn contribute to the explosive eruption and brecciation processes that occur during kimberlite magma emplacement and pipe formation.