Gravimetric preparation method is one of the most precise and accurate methods for preparing primary standard gas mixtures (PSMs). Although the principle and execution of the gravimetric method are not complicated, the uncertainty of the gravimetric method is so small that a seemingly minor error can result in an incorrect amount fraction of the PSM. Therefore, verifying the amount fraction of the PSMs is a necessary step. We perform a high-precision comparison between the PSMs of oxygen in nitrogen (∼100 µmol per mol) using a well-stabilized gas chromatograph with a thermal conductivity detector (GC-TCD) system in conjunction with high-precision pressure monitoring for sample amount correction and a quality-control cylinder technique in which the PSMs were analyzed against a reference cylinder, which leads to the cancellation of the drift in the sensitivity of the GC-TCD. After optimization of the measurement conditions, the relative expanded uncertainty reaches 0.022% (coverage factor k = 2), which is equivalent to the uncertainty of the PSMs. The Consultative Committee for Amount of Substance of the Comité International des Poids et Mesures performed a key comparison CCQM-K53, in which one of the PSMs used in this work was compared and agreed well with PSMs prepared by other National Metrology Institutes. These results show that the GC-TCD system developed in this work is sufficiently reliable, precise and accurate to verify PSMs.