The bis(1,2,6,7-tetracyano-3,5-dihydro-3,5-diiminopyrrolizinido)nickel(II) complex (NiL2, L = C11H2N7−) has been incorporated as dispersed monomer in polyvinylbutyral (PVB) at a fairly high concentration (0.021 M). NiL2/PVB spin coated thin films (thickness, ∼ 2 μm) on glass and silicon and evaporated free standing thicker films (thickness, ∼ 50 μm) have been studied by means of absorption or reflectivity visible as well as infrared spectroscopy. The light-blue NiL2/PVB film fades slightly on heating (for 7 min at 90 °C) and remains as such after cooling to room temperature. The optical spectrum of the thermally activated NiL2/PVB system, in contact with organic solvent vapors at room temperature, changes with time evolving towards the initial spectrum before the thermal treatment. The system is therefore amenable for sensing organic solvents in air. Several ordinary solvents have been tested. After 12 min exposure to air saturated with vapor a steady-state absorbance signal at the most sensitive wavelength (661 nm) is reached for any tested solvent. The system is most sensitive to alcohols. Response cycles are reported for methanol as solvent.