The dielectric barrier discharge ionization detector (BID) is one of the most modern detectors commercially available for gas chromatography (GC). Its technology based on the sample ionization through the energy released from the helium plasma generation process gives it the ability to act as a universal detector and a greater response to various types of compounds compared to the well-established flame ionization detector (FID). In this study, polycyclic aromatic hydrocarbons (PAHs), organophosphates (OPPs) and organochlorines pesticides (OCPs) were investigated. The parameters that could explain the performance of the BID and FID detectors were: structural factors, ionization energy (IE) and energy of the highest occupied molecular orbital (EHOMO), which were obtained by density functional theory (DFT). The relative (BID/FID) responses to PAHs and pesticides were about 1.8 and 3.0 times greater than FID, respectively. Less structural dependence of the BID signal compared to the FID signal was observed. Among the parameters calculated by DFT, the IE was the one that most seemed to have influenced the response of the two detectors studied. The theoretical data proved to be quite consistent to explain the trends observed experimentally, especially to the BID.