A polymer-bound dirhodium complex, [ {Rh-2( O2CCH3)(3)( Ds-pip)} n( O2C-P)], was prepared via ligand exchange of [ Rh-2( O2CCH3)(4)] with the side chains of a methyl methacrylate/ methacrylic acid copolymer ( O2C-P) followed by axial coordination of the fluorophore, N-dansylpiperazine ( Ds-pip). Emission from Ds- pip is quenched when coordinated to the dirhodium complex but can be restored upon displacement by analytes. Exposure of [ {Rh-2( O2CCH3)(3)( Ds-pip)}(n)( O2C-P)] films to aqueous nitric oxide ( NO) evokes a 2.2- fold increase in integrated emission. The polymer matrix excludes potentially interfering analytes including reactive oxygen or nitrogen species, which cannot readily permeate the film.