The application of IR 786 perchlorate (IR-786) as a selective optical sensor for cyanide anion in both organic solution (acetonitrile (MeCN), 100%) and solvent-free solid surfaces was demonstrated. In MeCN, IR-786 was selective to two anions in the following order: CN⁻ > OH⁻. A significant change in the characteristic dark green color of IR-786 in MeCN to yellow was observed as a result of nucleophilic addition of CN⁻ to the fluorophore, i.e., formation of IR 786-(CN), which was also verified by a blue shift in the 775 nm absorbance peak to 430 nm. A distinct green fluorescence emission from the IR-786-(CN) in MeCN was also observed, which demonstrated the selectivity of IR-786 towards CN⁻ in MeCN. Fluorescence emission studies of IR-786 showed that the lower detection limit and the sensitivity of IR-786 for CN⁻ in MeCN was 0.5 μM and 0.5 to 8 μM, respectively. The potential use of IR-786 as a solvent-free solid state sensor for the selective sensing and monitoring of CN⁻ in the environment was also demonstrated. On solvent-free solid state surfaces, the sensitivity of the IR-786 to CN⁻ in water samples was in the range of 50–300 μM with minimal interference by OH⁻.