A steady-state fluorescence (SSF) technique was used for studying the dissolution of UV-cured polymer films. These films are formed from poly(methyl methacrylate) (PMMA) chains labelled with pyrene, which was introduced as a fluorescence probe to monitor the dissolution processes. The PMMA films of various ethylene glycol dimethacrylate (EGDM) contents, cured by ultraviolet (UV) radiation, were dissolved in chloroform-heptane (20:80, v/v)mixtures. Dissolution of the films was monitored in real-time by the change in pyrene fluorescence intensity, I-P, in the solvent mixture. It was observed that the maximum pyrene intensity, I-Pinfinity, increased above a critical EGDM content, which was attributed to the formation of a percolation cluster, i.e. UV-cured films hardly dissolve above this critical EGDM content in the film. Desorption rates, D-d, were measured for films prepared with various EGDM contents. Copyright (C) 2002 John Wiley Sons, Ltd.