Massive graphite deposition resulting in volumetrically large occurrences in volcanic environments is usually hindered by the low carbon contents of magmas and by the degassing processes occurring during and after magma emplacement. In spite of this, two graphite deposits are known worldwide associated with volcanic settings, at Borrowdale, UK, and Huelma, Spain. As inferred from the Borrowdale deposit, graphite mineralization resulted from the complex interaction of several factors, so it can be considered as an example of self-organized critical systems. These factors, in turn, could be used as potential guides for exploration. The key factors influencing graphite mineralization in volcanic settings are as follows: (1) an unusually high carbon content of the magmas, as a result of the assimilation of carbonaceous metasedimentary rocks; (2) the absence of significant degassing, related to the presence of sub-volcanic rocks or hypabyssal intrusions, acting as barriers to flow; (3) the exsolution of a carbon-bearing aqueous fluid phase; (4) the local structural heterogeneity (represented at Borrowdale by the deep-seated Burtness Comb Fault); (5) the structural control on the deposits, implying an overpressured, fluid-rich regime favouring a focused fluid flow; (6) the temperature changes associated with fluid flow and hydration reactions, resulting in carbon supersaturation in the fluid, and leading to disequilibrium in the system. This disequilibrium is regarded as the driving force for massive graphite precipitation through irreversible mass-transfer reactions. Therefore, the formation of volcanic-hosted graphite deposits can be explained in terms of a self-organized critical system.