The interactions between trivalent Ce3+ ions with d(10) [Ag(CN)(2)] and d(8) [Pt(CN)(4)](2) ions in acetonitrile solutions has been studied by luminescence, ATR-FTIR, UV-vis spectroscopy and ab initio calculations. Addition of d8 or d10 cyano complexes to Ce3+ ions in acetonitrile gives strongly emissive solutions, suggesting the presence of new highly luminescent mixed-metal species. The great variability of the cyano compound MLCT excited state energies allow a tunability of the donor-acceptor resonance process. This results in selectivity of the emissive center and of the luminescence enhancement ability of the heterodimer. (C) 2009 Published by Elsevier B. V.