A method to measure the emissive concentration of 5-ethylidene-2-norbornene (ENB), a reactive compound used in industrial synthesis of terpolymers, has been developed. The starting points for the development of the presented method are European and Italian reference methods for the quantification of nonreactive volatile organic compounds in industrial emission. In this study, sampling conditions and desorption solvent have been optimized in laboratory and the method was applied in an industrial plant. The laboratory tests showed a good recovery (88-95%). The concentrations of ENB in industrial emission obtained with the developed method were compared with an online gas chromatography-flame ionization results (R (2) > 0.97). In addition, several manual measurements were performed in parallel, and the resulting %RSD repeatability was <9%. The developed method provides a discontinuous technique to measure reactive volatile organic compounds using easy-to-use instruments and assures a very good accuracy and precision even with high-humidity gas flows. The method could be extended to other reactive compounds of the same class.