In this work we used the sol–gel technique to develop luminescent Eu(III) transparent films deposited on glass slides to build for sensor devices capable of monitoring transition metal ions in aqueous solutions. The films were obtained from a bis(trialkoxysilyl) organic precursor synthesized from the amide of the 2,6-pyridinedicarboxylic acid (DPA) with aminopropyltriethoxysilane (APTES) in the presence or absence of cetyl trimethyl ammonium bromide (CTAB) surfactant as templating agent and triethylethoxysilane (TEOS) as crosslinker. These sensor devices were used to perform in situ quenching experiments by Cu(II), Fe(III), Co(II) and Ni(II) ions. The results indicate that the templated films allow the detection and quantification of these metals down to ppb levels by means of the values of the Stern–Volmer constants. In particular, it was shown that Cu(II) acts as an extremely efficient quencher ( K SV = 3.5 × 10 5 M −1) when compared with the results obtained for the other metals, opening the possibility to use these devices as potential Cu(II) sensors for actual applications in aqueous media.