We focus on the collision dissociation process of O2+O2→O+O+O2 at high temperatures (8000 K–30000 K). The research method is the new general non-equilibrium dynamics model proposed by Singh et al. The model parameters are determined by calculating the dissociation probability under the specific vibrational energy and the energy distribution functions in the quasi-steady state (QSS). It is found that the dissociation rate is more easily at high vibrational energy levels. Moreover, the energy distribution function deviates from the Boltzmann distribution in the QSS state. We obtain the dissociation rate coefficients at high temperatures by integrating the dissociation probability and the internal energy distribution functions (the Boltzmann distribution, the QSS state distribution, and the non-Boltzmann distribution). Our results demonstrate that the rate coefficients depend on the vibrational temperature and more strongly at a lower translational temperature.