Solid-state Ln-L compounds, where Ln stands for light trivalent lanthanide (La to Gd, except Pm) and L is glycolate (C2H3O3) have been synthesized. Characterization and investigation were made by means of complexometry, X-ray diffractometry, Fourier transform infrared spectroscopy (FFIR), simultaneous thermogravimetry and differential scanning calorimetry (TG-DSC), and TG-DSC coupled to FFIR. All the compounds were obtained in the anhydrous state. The thermal decomposition of the anhydrous compounds occurs in a single, three, four or five steps and the final residue was CeO2, Pr6O11 and Ln(2)O(3) (Ln = La, Nd to Gd). The results also provide information concerning thermal behavior and identifications of the gaseous products evolved during the thermal decomposition of these compounds. Furthermore, the theoretical and experimental spectroscopic data suggest the possible modes of coordination of the ligand with the metals. (C) 2014 Elsevier B.V. All rights reserved.