A template-assisted sol-gel procedure was developed and optimised for the preparation of silica thin films embedding the fluorescent dye 3(dansylaniido)-propyl-triethoxysilane (DNS-APTES) for Cu(II) sensing purposes. The different parameters involved (solution composition, nature of the template, deposition and annealing conditions, post-synthesis deposition of additional coatings, etc.) were independently changed in order to evaluate their effect on the final microstructure, composition and sensor performances of the films. The optirmisation procedure encompassed also the choice of the suitable parameters to ensure stability of the sensing films and to avoid the leaching of the fluorescent dye. Films prepared by using the non-ionic surfactant F127, without an additional coating and with a post-deposition annealing at 100 degrees C for 2 h, were proven to be the best performing ones, characterised by the largest and fastest fluorescence quenching. In particular, the presence of a template Was demonstrated to play a major role in determining the efficiency of the sensing device. The surface and in-depth composition of thin films was analysed by X-Ray Photoelectron Spectroscopy (XPS) and Secondary Ion Mass Spectrometry (SIMS). The sensing performances of the films were tested by fitration experiments with CU2+. (c) 2007 Elsevier B.V. All rights reserved.