To achieve the analysis of polychlorinated biphenyl (PCB) indicators in soil with complicated matrix, three mass spectrum detection techniques, such as gas chromatography quadrupole mass spectrometry (GC Q-MS), GC time-of-flight (GC TOF-MS) and comprehensive two-dimensional TOF (GC×GC TOF-MS) were applied. It showed that GC Q-MS failed to detect the targets; GC TOF-MS could analyze two of the targets and detect the characteristic ions of another 4 target compounds; GC×GC TOF-MS could precisely separate 7 indicators of PCBs with high matched results, simultaneously it could detect the other 20 PCBs, some pesticides and polycyclic aromatic hydrocarbons. It revealed that compared with Q-MS, TOF-MS is the higher analysis technique for detection and GC × GC TOF-MS has the most powerful separation ability, the highest sensitivity and resolution.