The Calatrava Volcanic Field (CVF) of Castilla-La Mancha is characterised by numerous monogenetic volcanic centres, that erupted mainly foidites, melilitites and carbonatites (ultra-alkaline rock-association sensu, Le Bas, 1981) carrying abundant mantle xenoliths. At CVF, carbonatites have been described by Bailey et al. (2005) and Stoppa et al. (2011). Along with the volcanic field of Eifel of Germany, Limagne basin of France and Intra-mountain Ultra-alkaline Province (IUP) of Italy, the CVF encompasses the most numerous PlioceneQuaternary extrusive carbonatites in Western Europe in terms of dimension, number and size of volcanoes (Bailey et al., 2005; Bailey et al., 2006). Similar volcanic fields are ToroAkole and Bufumbira in Uganda (Bailey & Collier, 2000), the Avon district in Missouri (Callicoat et al., 2008), Mata da Corda in Brazil (Junqueira-Brod et al., 1999) and West Qinling in Gansu Province, China (Yu et al., 2003). In spite of abundant local studies (Gonzalez Cardenas et al., 2010; Peinado et al., 2009), the CVF has been mostly neglected by the international audience, although Bailey (2005) outlined the need for a long-term research program on CVF. This work focuses on the role of deep CO2 at CVF, which is considered an intrinsic component of carbonatitic mantle magmatism (Hamilton et al., 1979). Previous, studies of CVF volcanoes considered that the hydrovolcanism is a necessary and sufficient condition to explain the CVF volcanological features, and, as a corollary that the carbonate present in the pyroclastic rocks is remobilised limestones (e.g., Lopez-Ruiz et al., 2002). We propose an alternative hypotheses based on CO2 violent exolution and expansion germane to diatremic propagation of ultra-alkaline melts towards the surface and to dry-magmatic origin of the maars (Mattsson & Tripoli, 2011; Stoppa, 1996; Stoppa & Principe, 1998).