The solvent-free conversion of N-carbamoyl-L-proline to hydantoin-L-proline by direct heating at 470 K is reported. A reaction mechanism is proposed based on a nucleophilic intramolecular substitution reaction involving both the lone pair of the NH2 group and the carboxylic acid group of the N-carbamoyl-L-proline. The DSC and TGA experiments show rising of the baselines of the curves prior to melting and decomposition given evidence of the onset of the thermal reaction. NMR experiments were used to identify the product of the reaction, hydantoin-L-proline, whose crystal structure was obtained from X-ray synchrotron powder diffraction data collected on the solidified melt. This compound displays a crystal packing directed by hydrogen bonds forming a layered structure pile up along the c direction.