The synthesis of a quinoxaline-appended aza-macrocyclic ligand together with corresponding LnIII complexes are described. The luminescence properties of the complexes show that the quinoxaline unit sensitises both visible (EuIII) and near-IR (NdIII and YbIII) emitting lanthanide ions. UV–Vis absorption and time-resolved photophysical studies together with X-ray structural data suggest that as well as contributing chromophorically, the quinoxaline moiety generally participates in the first coordination sphere of LnIII. The luminescent pH response of the EuIII complex is also reported. The form of the steady state spectrum changes profoundly in the pH range 2–12, implying a change in the coordination environment, which was confirmed with time-resolved lifetime measurements that suggest an increase in europium inner sphere hydration at acidic pH.