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The reflectance spectrum of solid MeReO 3 (trans-4-styrylpyridine) shows a long-wavelength band (λ max = 342 nm) with vibrational structure. This band is assigned to an intraligand transition of the coordinated styrylpyridine. In solution (e.g. CH 2 Cl 2 ) the complex largely dissociates into MeReO 3 and styrylpyridine which displays a broad absorption at λ max = 308 nm. Irradiation with 366 nm light leads to selective excitation of residual amounts of intact MeReO 3 (trans-4-styrylpyridine) which undergoes a complete trans-to-cis photoisomerization of the coordinated ligand. Owing to the kinetic liability of MeReO 3 (trans-4-styrylpyridine) this photolysis proceeds as a photoassisted reaction of 4-styrylpyridine.