Ruthenium complexes involving sulfoxide ligands can undergo linkage isomerization upon light absorption, accompanied by dramatic changes in their optical properties. These remarkable photochromic properties are sensitive to the nature of the ligand as well as to that of the solvent. We used tandem ion mobility spectrometry coupled to mass spectrometry to gain direct experimental insight into the isomerization pathways connecting the different linkage isomers of an isolated ruthenium complex with two dimethyl-sulfoxide ligands. We find that the isomerization behavior of the solvent-free complex differs from that previously reported in the solution-phase, which is in line with recent theoretical predictions.