Detailed information has been obtained on the structure of pure and aquated complexes in AgCl using multifrequency EPR and powder ENDOR spectroscopy. Because of the anisotropy of the centre g matrix it was possible to selectively excite centres with a specific angle between the z axis of the g matrix and the magnetic field axis. As a result, almost single-crystalline-like ENDOR spectra were obtained and the angular dependence of the ENDOR spectra could be obtained by scanning the magnetic field over the range of the EPR spectra. Three different centres were detected that are distinguished by different thermal stabilities, different parameters of the g matrix and the hyperfine matrices of the central Rh nucleus and ligand H, Cl and Ag nuclei. A pure centre without ligands could only be generated in an emulsion where great care was taken to prevent the aquation of the dopant ion in the dopant solution and during the precipitation. This centre had the highest thermal stability. In an emulsion prepared conventionally two centres were found that are associated with one and two ligands bound to the ion in the plane perpendicular to the g matrix z axis. Using the results of the EPR and ENDOR analysis in combination with the results of a total energy calculation two models are proposed that contain the positions of the ligands and the charge compensating vacancies.