e aim of this paper is to propose a stochastic method for estimating the detection limits (DLs) and quantitation limits (QLs) of compounds registered in a database of a GC/MS system and prove its validity with experiments. e approach described in ISO 11843 Part 7 is adopted here as an estimation means of DL and QL, and the deca uorotriphenylphosphine (DFTPP) tuning and retention time locking are carried out for adjusting the system. Coupled with the data obtained from the system adjustment experiments, the information (noise and signal of chromatograms and calibration curves) stored in the database is used for the stochastic estimation, dispensing with the repetition measurements. Of sixty-six pesticides, the DL values obtained by the ISO method were compared with those from the statistical approach and the correlation between them was observed to be excellent with the correlation coe cient of 0.865. e accuracy of the method proposed was also examined and concluded to be satisfactory as well. e samples used are commercial products of pesticides mixtures and the uncertainty from sample preparation processes is not taken into account.