Mediterranean climate regions have become more vulnerable to fire due to the extreme weather conditions and numerous Eucalyptus globulus plantation areas. The aim of this study is to analyze the fire hazard related to E. globulus in a forest fire scenario, based on the contrast of thermochemical parameters and their relationship with chemical properties, considering the predominant exotic forest species (E. globulus, Pinus radiata, Acacia dealbata, and Acacia melanoxylon) present in the Valparaiso region, Chile. The results revealed that although all of the studied species were highly flammable, E. globulus was extremely flammable, as its leaves contain high concentrations of essential oils, monoterpenes, and sesquiterpenes, which can generate a flammable atmosphere due to their low flashpoint and the strong negative influence shown between the essential oils, volatile terpenes, and limonene concentration. Moreover, the heat of combustion of E. globulus was positively correlated with its high essential oil contents. Finally, all of the studied species had low flashpoints and high heating values; therefore, they are predisposed to ignite in the presence of a heat source, releasing high amounts of energy during combustion, which contributes to the risk of the formation and spread of canopy fires among these tree formations.