Thermoanalytical techniques are currently used for the analysis of additives contained in polymers that cannot be easily dissolved, extracted, or hydrolyzed. With these techniques, the polymers are heated to liberate the additives trapped in the polymer matrix. If the polymer is heated slowly, up to its thermal degradation, the technique is called temperature-programmed pyrolysis (TPPy). For TPPy experiments, mass spectrometry is generally used as the detection method. The ionization sources commonly used in mass spectrometry, such as CI and EI, can cause fragmentation during the ionization process. Fragmentation decreases the sensitivity of the molecular ions and increases the risks of interferences with the compounds coming from the matrix. An energy-tunable ionization technique, called metastable atom bombardment (MAB), is proposed for TPPy/MS experiments. With this ionization source, the energy of ionization depends on the metastable gas used. With low-energy metastable gases such as Xe or N(2), fragmentation is reduced compared to CI, whereas with medium-energy metastable gases such as Ar or Kr, the fragmentation is similar to that observed with CI. TPPy/MAB-MS was performed on an unknown polyurethane-based car paint. The detection of molecular ions and characteristic fragments with MAB(N(2)) led to the identification of two light stabilizers: Bis(1,2,2,6,6-pentamethyl-4-piperidinyl)sebacate (BPPS) and 2-(2H-benzotriazol-2-yl)-4,6- di-tert-pentylphenol (PTPP). Using MAB(Ar) to simulate CI, the molecular ion and one of the two characteristic fragments of BPPS were not detected, thus confirming the advantage of using MAB(N(2)) ionization for TPPy/MS experiments.