In this work, efficient trans ⇌ cis photoswitchings of 4-(4-cyano)styrylpyridine (stpyCN) coordinated to organometallic bipyridyl tricarbonyl rhenium(I) complexes, fac-[Re(CO)3(NN)( trans-stpyCN)]+, where NN = 2,2'-bipyridine (bpy) or 4,4'-dimethyl-2,2'-bipyridine (dmb), are described. For both complexes, the true trans-to- cis quantum yields determined by 1H NMR spectroscopy are similar at 313, 334, and 365 nm irradiations (Φ trans→ cistrue(313-365 nm) ∼ 0.45), with a small decrease at 404 nm (Φ trans→ cistrue(404 nm) ∼ 0.37). The investigated complexes also exhibit significant quantum yields for the reversible cis-to- trans photoreactions (Φ cis→ trans(255 nm) = 0.22). The luminescent properties of these complexes were also analyzed in different media to elucidate a key role of the 3ILstpyCN state in photophysical and photochemical processes, giving new insights on their intriguing photobehavior.