The 4-(1-naphthoate)-2,2,6,6-tetramethylpiperidine-1-oxyl (NfO-TEMPO) has been synthesized and successfully grafted in the melt onto a random poly(ethylene-co-1-ottene) copolymer. Functionalized polyolefins have been prepared by coupling reaction between NfO-TEMPO free radicals and macroradicals which have been formed by H-abstraction induced by the presence of a peroxide. In order to deepen insight into the functionalization mechanism, the reaction has been investigated by Electron Paramagnetic Resonance (EPR). EPR spectra collected during the reaction run, have evidenced the decrease of TEMPO signal as a consequence of temperature increasing. This decrease has been attributed to the formation of a covalent bond between macroradicals and nitroxide free radical. The resulting functionalized polyolefins. PO-g-(NfO-TEMPO), have been characterized by FT-IR and H-1 NMR which has allowed to evaluate their functionalization degree, whereas UV-Vis and fluorescence spectroscopy have been used to investigate their optical properties. The comparison with low molecular weight model compounds, has allowed to state that our methodology can be conveniently adopted to prepare fluorescent polyolefins where the optical properties of the chromophore has been completely transferred to polymer backbone both in solution and in the condensed phase. (C) 2012 Elsevier Ltd. All rights reserved.