Ligand exchange reactions between [Cp*Ru(NCMe)3][PF6], where Cp* represents η5-C5Me5, and the polycyclic aromatic hydrocarbons (PAHs) pyrene, acenaphthylene and fluoranthene afforded the known [Cp*Ru(η6-pyrene)][PF6] (1) and the new mixed sandwiches [Cp*Ru(η6-acenaphthylene)][PF6] (2) and [Cp*Ru(η6-fluoranthene)][PF6] (3), respectively, isolated in quantitative yields (94–100%). Complex 3 is formed as a mixture of two isomers: 3A as the major product where the [Cp*Ru+] moiety is coordinated to the naphthalene fragment of fluoranthene, and 3B with the coordination of the arenophile to the peripheral benzene ring, in a 90/10 spectroscopic ratio. The composition and identity of the complexes were deduced by elemental analysis, 1H and 13C multidimensional NMR spectroscopy, and mass spectrometry. Compounds 1A, 3A and 2A have been characterized using X-ray structural investigations. That showed that the [Cp*Ru+] unit is η6-attached to one of the two naphthalene rings in each complex. Heating 1 and 3 at 90 °C in CD3NO2 solutions or heating 3 at 120 °C in the solid phase did not provide any evidence for thermally induced intramolecular inter-ring haptotropic rearrangements. These rearrangements were modelled by DFT calculations which indicated rather high activation energies.