The rational design of rare-earth doped materials represents one of the major goals of current research in the field of optoelectronics. In this study, ZnO:Er(III) nanosystems were synthesized by means of a hybrid rf-sputtering/sol-gel (SG) route, consisting of the erbium (guest) rf-sputtering on porous zinc oxide xerogels (host) obtained by the SG method, followed by ex situ thermal treatments in air (300-600 degrees C, 1-5 h). Particular attention was focused on tailoring the erbium content and distribution in the resulting systems by optimization of the processing conditions. The structural, morphological, and compositional characteristics and their interplay with the synthesis procedure were investigated by glancing incidence x-ray diffraction, x-ray photoelectron spectroscopy, x-ray excited Auger electron spectroscopy, secondary ion mass spectrometry, UV-visible-near IR absorption spectroscopy, and atomic force microscopy. The obtained results highlight the advantages and versatility of the adopted preparation strategy in tailoring the amount and distribution of Er(III) species in high purity ZnO matrices, resulting in nanosystems endowed with compositional and morphological homogeneity at nanoscale level. (c) 2006 American Vacuum Society.