Essential oils from the two most representative shrub species from the Iberian Peninsula (namely Cistus ladanifer L. and Erica arborea L.) have been characterized by Fourier transform infrared spectroscopy (FTIR) and thermoanalytical techniques (TG/DTG and DSC). Vibrational spectra have been compared with those of components of the plants, and with those of oils, gums and resins from other species. The different content in terpenoids of C. ladanifer oil (mainly mono- and- sesquiterpenoids) and E. arborea oil (mainly triterpenoids) is reflected in the ATR-FTIR by the position of the bands at around 2873 cmf⁻¹, 1730 cm-⁻¹ and 1678 cm⁻¹ As regards their thermal behavior, C. ladanifer-derived oil evinced higher thermal stability than that of obtained from E arborea: the pyrolysis of the former was sensitized at 210°C, whereas for the later it occurred at 143°C. These temperatures are high enough to state that thermolabile constituents such as terpenoids are conserved in the hydrodistillation and that this extraction process ensures the recovery of the main constituents of both-essential oils.