In this work, AlNxOy thin films were deposited by reactive magnetron sputtering, using an aluminum target and an Ar/(N2+O2) atmosphere. The DC magnetron discharge parameters during the deposition process were investigated by optical emission spectroscopy and a plasma floating probe was used. The discharge voltage, the electron temperature, the ion flux and the optical emission lines were recorded for different reactive gas flows, near the target and close to the substrate. This information was correlated with the structural features of the deposits as a first step in the development of a system to control the structure and properties of the films during reactive magnetron sputtering. As the target becomes poisoned, the discharge voltage suffers an important variation, due to the modification of the secondary electron emission coefficient of the target, which is also supported by the evolution of the electron temperature and ion flux to the target. The sputtering yield of the target was also affected, leading to a reduction of the amount of Al atoms arriving to the substrate, according to optical emission spectroscopy results for Al emission line intensity. This behavior, together with the increase of non-metallic elements in the films, allowed obtaining different microstructures, over a wide range of compositions, which induced different electrical and optical responses of films. ; This research was supported by FEDER through the COMPETE Program and by the Portuguese Foundation for Science and Technology (FCT) in the framework of the Strategic Project PEST-C/FIS/UI607/2011. J. Borges also acknowledges FCT financial support under PhD grant N?? SFRH/BD/47118/2008 (financiado por POPH ??? QREN ??? Tipologia 4.1 ??? Forma????o Avan??ada, comparticipado pelo Fundo Social Europeu e por fundos nacionais do MCTES).