In this paper the solid-state transformations under heating of cis-[Ir(CO)(2)Cl(C5H5N)] are discussed. The complexity of the transformations was revealed by integrating infrared spectroscopy. conventional and bidimensional X-ray diffraction, thermal analysis, and hot stage optical microscopy. During heating anisotropic expansion of the lattice along the Ir-Ir stacking takes place. Then cis-[Ir(CO)(2)Cl(C5H5N)] undergoes an irreversible solid-solid phase transition to a lattice of higher symmetry followed by a reversible transition into the amorphous phase. Under proper cooling a partial recrystallization takes place. Experiments in the presence of oxygen must be carried out in short time periods to avoid oxidation from Ir(I) to Ir(III).