chemical ionization (NICI), and the results were compared with those from GC coupled with high-resolution MS (HRMS) with electron impact (EI). The recovery rates of the surrogate PCB congeners were 97.2%–112% (coefficient of variation: 5.3%–8.5%), and the method detection limits for PCBs in each matrix obtained by GC–NICI–quadrupole mass spectrometry (qMS) were 1.9–20 pg g−1 wet wt. The analytical values of the target compounds in the samples analyzed by GC–NICI–qMS and GC–EI–HRMS were comparable (Passing–Bablok regression: R = 0.888–0.967), and the analytical values obtained via GC–NICI–qMS were almost comparable with those of the certified serum samples from National Institute of Standards and Technology (NIST: SRM1957), indicating that GC–NICI–qMS is suitable for the analysis of tetra- to hepta-chlorinated PCBs in serum samples.