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A method to empirically determine the gaseous emissions produced from a pyrotechnic flare composition through the combination of gas chromatography and mass spectrometry is described. In this approach, milligram quantities of a model yellow signal flare composition and its individual polymeric constituents were subjected to pyrolysis at conditions that were guided via thermal analysis. Many volatile organic compounds and polycyclic aromatic hydrocarbons were identified as emission products even though thermochemical calculations fail to anticipate such products. Thus, these data may complement characterization of emission products predicted in silico. Pyrolysis of this pyrotechnic composition also demonstrated unique products formed via donation of nitrogen to aromatic fragments originating from resinous portions of the formulation. These products included EPA priority pollutants that were not formed by decomposition from staple ingredients. This work demonstrates that a variety of EPA priority pollutants...