Thermoanalytical (differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), thermogravimetric analysis coupled with Fourier transform infrared spectroscopy (TG/FTIR)) and spectroscopic (X-ray diffraction (XRD), ultraviolet-visible (UV-Vis), mass spectrometry (MS) and Fourier transform infrared diffuse reflectance (DRIFT) measurements have been used to characterise solid-state retinoic acid (RA) from a chemico-physical point of view. Between 130 and 160 degrees C, a phase transition takes place that does not correspond to the transition between the known monoclinic and triclinic phases (DSC and XRD evidence). By annealing in air (in the 130-160 degrees C temperature range and for different times), an exothermic oxidative degradation occurs that, depending on the thermal treatment, competes with the mentioned phase transition (TGA evidence). Spectroscopic techniques (UV-Vis, MS and DRIFT) allow one to conclude that the new solid phase is still constituted by retinoic acid with a different orientation of the side chain. Finally, RA does not undergo stable melting: the fragmentation patterns, both in air and in nitrogen, have been examined by TG/FTIR.