In this study, we investigated the effect of various O2 concentrations, from 20% to 90%, in nitrogen–oxygen ( N2/O2 ) mixtures on the characteristics of secondary streamers. As oxygen molecules have different molecular characteristics from nitrogen molecules in terms of ionisation threshold and electron attachment property, streamer discharges generated under various nitrogen–oxygen ratios may exhibit differing characteristics such as electron density, electric field, and radical formation. We focused on the changes in these parameters in secondary streamers using simulations. Simulations were first performed under the same conditions as those in previous experiments to compare the results of the ozone production, discharge current, and discharge emission characteristics. To compare the ozone production characteristics, simulated O radicals–the precursor of ozone–were used in the simulation for simplicity. This comparison showed that, although the absolute values of each parameter were different, the simulation exhibited a similar trend in the case of the experimentally obtained oxygen concentration dependence. After the validity of the simulation was verified to some extent via a comparison with the experiment, the results obtained from the simulation were analysed in detail. The results showed that, although the electric field strength in the secondary streamer did not change much as the oxygen concentration increased, the decrease rate of the electron density was greatly accelerated by the electron attachment reaction of oxygen. As a result, many of the electrons had already dissipate during the development of the primary streamer, and few electrons remained when the secondary streamer was formed. This effect suggests that the ratio of the amount of O radicals produced in the primary streamer to that produced in the secondary streamer changes as the oxygen concentration changes.