Biomass provides potential benefits for obtaining value-added compounds instead of straight burning; as Chile has forestry potential that supports such benefits, it is crucial to understand the biomasses’ properties and their thermochemical behaviour. This research presents a kinetic analysis of thermogravimetry, and pyrolysis of representative species in the biomass of southern Chile, heating biomasses at 5 to 40 °C·min⁻¹ rates before being subjected to thermal volatilisation. The activation energy (Ea) was calculated from conversion using model-free methods (Flynn–Wall–Ozawa (FWO), Kissinger–Akahira–Sunose (KAS), and Friedman (FR)), as well as the Kissinger method based on the maximum reaction rate. The average Ea varied between KAS 117 and 171 kJ·mol⁻¹, FWO 120–170 kJ·mol⁻¹, and FR 115–194 kJ·mol⁻¹ for the five biomasses used. Pinus radiata (PR) was identified as the most suited wood for producing value-added goods based on the Ea profile for the conversion (α), along with Eucalyptus nitens (EN) for its high value of reaction constant (k). Each biomass demonstrated accelerated decomposition (an increase in k relative to α). The highest concentration of bio-oil containing phenolic, ketonic, and furanic compounds was produced by the forestry exploitation biomasses PR and EN, demonstrating the viability of these materials for thermoconversion processes.