XAFS, IR, and UV-vis (diffuse reflectance and photoluminescence) spectroscopies have been employed to investigate the local environment of Cu-I in Cu-I-ZSM-5 prepared by gas phase reaction of H-ZSM-5 (SiO2/Al2O3 = 90-50) with CuCl. The measurements confirm that the absolutely predominant copper species formed with this procedure are Cu-I:Cu species in other oxidation states are less than 1%. Direct proof of the absence of both unreacted CuCl microaggregates and of copper clusters in the zeolite channels is also given. Cu-I-ZSM-5 prepared in this way represents a model solid for investigating the structure of isolated Cu-I sites in zeolites. EXAFS analysis reveal that, in vacuum conditions, Cu+ cations are surrounded by 2.5 +/- 0.3 oxygens at 2.00 +/- 0.02 Angstrom. The combined use of EXAFS, IR, and photoluminescence UV-vis spectroscopies and computer graphic simulations allows to infer that Cu+ ions in Cu-I-ZSM-5 are located in two families of sites, indicated as I and II, (site II having the highest coordinative unsaturation) which are nearly equipopulated at RT. The formation of Cu+-(CO)(n), (n = 1, 2) adducts at RT is observed by IR and supported by XAFS spectroscopies. At similar or equal to 110-120 K, the Cu-I of family II adsorbs up to three CO molecules with formation of Cu-I-(CO)(3) cis-carbonyl complexes; copper(I) in sites I are less unsaturated and can form only cis-Cu-I-(CO)(2). Both sites form, at similar or equal to 110-120 K, stable cis-Cu-I-(NO)(2) species. IR spectroscopy gives evidence of the N-2 interaction with both families of sites at similar or equal to 110-120 K : the formation of stable Cu-I(N-2) adducts even at RT.