Forest fires are one of the main environmental threats in Chile. Fires in this Mediterranean climate region frequently affect native forests and exotic plantations, including in several cases urban and rural settlements. Considering the scarcity of information regarding the fire response dynamics of tree species that are frequently affected by fires, this study aims to establish a flammability classification according to the evolution of the fire initiation risk presented by the most affected forest species in the Valparaíso region. Three exotic species, Eucalyptus globulus, Pinus radiata, and Acacia dealbata, and two native species, Cryptocarya alba and Quillaja saponaria, were studied. Flammability assays indicate that E. globulus, A. dealbata, and C. alba are extremely flammable, whereas P. radiata and Q. saponaria are flammable. Furthermore, E. globulus and A. dealbata have the highest heating values while Q. saponaria has the lowest values. The extreme flammability of E. globulus, A. dealbata, and C. alba indicates a high susceptibility to ignite. Furthermore, the high heat of combustion of E. globulus and A. dealbata can be associated with a high energy release, increasing the risk of fires spreading. In contrast, Q. saponaria has the lowest predisposition to ignite and capacity to release heat. Accordingly, this work shows that all studied tree species contain organic metabolites that are potentially flammable (sesquiterpenes, aliphatic hydrocarbons, alcohol esters, ketones, diterpenes, and triterpenes) and can be considered as drivers of flammability in vegetation. Finally, these preliminary results will aid in the construction of more resilient landscapes in the near future.