In this study, we assess the applicability of different analytical techniques, namely, direct probe (DP), gas chromatography (GC), and comprehensive two-dimensional gas chromatography (GC × GC) coupled to atmospheric pressure chemical ionization (APCI) with a high resolution (HR)-time-of-flight (TOF)-mass spectrometry (MS) for the analysis of flame retardants and plasticizers in electronic waste and car interiors. APCI-HRTOFMS is a combination scarcely exploited yet with GC or with a direct probe for screening purposes and to the best of our knowledge, never with GC × GC to provide comprehensive information. Because of the increasing number of flame retardants and questions about their environmental fate, there is a need for the development of wider target and untargeted screening techniques to assess human exposure to these compounds. With the use of the APCI source, we took the advantage of using a soft ionization technique that provides mainly molecular ions, in addition to the accuracy of HRMS for identification. The direct probe provided a very easy and inexpensive method for the identification of flame retardants without any sample preparation. This technique seems extremely useful for the screening of solid materials such as electrical devices, electronics and other waste. GC-APCI-HRTOF-MS appeared to be more sensitive compared to liquid chromatography (LC)-APCI/atmospheric pressure photoionization (APPI)-HRTOF-MS for a wider range of flame retardants with absolute detection limits in the range of 0.5-25 pg. A variety of tri- to decabromodiphenyl ethers, phosphorus flame retardants and new flame retardants were found in the samples at levels from microgram per gram to milligram per gram levels.