Two [(bpy)Re(CO)₃L]⁺ complexes (bpy = 2,2′-bipyridine), where L contains an aza-15-crown-5 ether which is linked to Re via an alkenyl- or alkynyl-pyridine spacer, have been synthesised along with model complexes. Solutions of the complexes in acetonitrile have been studied by UV-Vis absorption spectroscopy, and by 1D and 2D ¹H NMR spectroscopy. Strong UV-Vis bands, assigned to intraligand charge-transfer transitions localised at the L ligands, blue shift on protonation of the azacrown nitrogen atom or on complexation of alkali-metal (Li⁺, Na⁺ and K⁺) or alkaline-earth metal (Mg²⁺, Ca²⁺ and Ba²⁺) cations to the azacrown; the magnitude of the blue shift is dependent on the cation, with protonation giving the largest shift of ca. 100 nm. Cation binding constants in the range of log K = 1–4 depend strongly on the identity of the metal cation. Protonation or cation complexation causes downfield shifts in the ¹H NMR resonances from most of the azacrown and L ligand protons, and their magnitudes correlate with those of the blue shifts in the UV-Vis bands; shifts in the azacrown ¹H NMR resonances report on how the different metal cations interact with the macrocycle. UV-Vis and ¹H NMR spectra of the free L ligands enable the effect of the Re centre to be assessed. Together, the data indicate that the alkene spacer gives a more responsive sensor than the alkyne spacer by providing stronger electronic communication across the L ligand.