In this study, the analytical compatibility of the gas chromatographic (GC) approach was evaluated through a cross-calibration exercise. To this end, three aromatic volatile organic compounds (VOCs: benzene, toluene, and p-xylene (BTX)) were simultaneously analyzed with four individual instrumental setups (type I = GC with MS plus solid phase microextraction (SPME) method, II = GC with flame ionization detection (FID) plus SPME, III = fast GC-FID plus SPME, and IV = GC-FID plus air server/thermal desorption (AS/TD) method). A comparison of basic quality assurance (QA) data revealed considerable differences in DL values among the methods with moderate variabilities in the intercompound sensitivity. In light of the differences in detection properties, the analytical bias involved for each methodological approach was assessed by the relative relationship between analytes and basic operating conditions. The results suggest that the analysis of environmental samples at ultra-low concentration levels (at or below ppb level) can be subject to diverse sources of bias. Although detection properties of target compounds seem to be affected by the combined effects of various factors, changes in the sample concentration levels were seen to be the most consistent under the experimental setups analyzed in this study.