Plastics are complex mixtures consisting of a polymer and additives with different physico-chemical properties. We developed a broad screening method to elucidate the nature of compounds present in plastics used in electrical/electronic equipment commonly found at homes (e.g., electrical adaptors, computer casings, heaters). The analysis was done by (a) solvent extraction followed by liquid chromatography coupled to high accuracy/resolution time-of-flight mass spectrometry (TOFMS) with different ionization sources or (b) direct analysis of the solid by ambient mass spectrometry high accuracy/resolution TOFMS. The different ionization methods showed different selectivity and sensitivity for the different compound classes and were complementary. A variety of antioxidants, phthalates, UV filters, and flame retardants were found in most samples. Furthermore, some recently reported impurities or degradation products derived from flame retardants were identified, such as hydroxylated triphenyl phosphate and tetrabromobisphenol A monoglycidyl ether.