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We evaluated the thermogravimetric and devolatilization rates of hemicellulose and cellulose, and the calorimetric behavior of the torrefied biomass, of five tropical woody species (Cupressus lusitanica, Dipteryx panamensis, Gmelina arborea, Tectona grandis and Vochysia ferruginea), at three temperatures (TT) and three torrefaction times (tT) using a thermogravimetric analyzer. Through a multivariate analysis of principal components (MAPC), the most appropriate torrefaction conditions for the different types of woody biomass were identified. The thermogravimetric analysis-derivative thermogravimetry (TGA-DTG) analysis showed that a higher percentage of the hemicellulose component of the biomass degrades, followed by cellulose, so that the hemicellulose energy of activation (Ea) was less than that of cellulose. With an increase in TT and tT, the Ea for hemicellulose decreased but increased for cellulose. The calorimetric analyses showed that hemicellulose is the least stable component in the torrefied biomass under severe torrefaction conditions, and cellulose is more thermally stable in torrefied biomass. From the MAPC results, the best torrefaction conditions for calorimetric analyses were at 200 and 225 °C after 8, 10, and 12 min, for light and middle torrefaction, respectively, for the five woody species.