The dependence of the luminescence of lanthanide cryptates on the interaction with the environment is examined. It is shown that anionic species can influence the luminescence by either entering the first coordination sphere of the metal ion or by giving rise to bimolecular processes. These effects are investigated on systems containing Eu3+ or Tb3+ cryptates and iodide or phosphate anions. The results are discussed on the basis of the nature of the lanthanide ion and the ligand-metal interaction in the excited state.