A series of bidentate allene- and enyne-containing ligands have been synthesized and the photochemical properties of their rhenium(I) complexes have been studied. These complexes exhibit facile isomerization of the conjugated double bonds upon ambient light exposure. Simulations unveiled a very efficient intersystem crossing and the consequent key role of the triplet states in the observed photochemistry of these substrates upon rhenium(I) complexation.