Abstract Valence tautomer transition occurs mainly in 3d metalorganic complexes with redox-active ligands and makes them potential candidates for single-molecular switches. The transition occurs under temperature, pressure, or light-induced stimuli and is strongly affected by the intermolecular interactions. However single-crystal x-ray diffraction is not always applicable to such systems when crystal structure is destroyed upon transition or system is studied in the solution. Such an example is bis(o-semiquinonato) cobalt complex with TEMPO-functionalized iminopyridine ancillary ligand. In this work we apply two complementary techniques—ligand-sensitive Fourier transform infrared spectroscopy (FTIR) and metal sensitive Co K-edge x-ray absorption spectroscopy (XAS). In a solid state, a temperature hysteresis of magnetization larger than 40 K was observed upon cyclic cooling-heating. So, the temperature of phase transition upon cooling is about 40 K lower than that upon heating. In solution, the x-ray absorption spectra for high-temperature and low-temperature states were similar to that in the solid form, but the hysteresis was absent. Two methods are can probe valence tautomer transition, but XAS has an advantage for the liquid phase analysis and FTIR has larger sensitivity to the ligand related interactions in solid.