Vibrational relaxation of oxygen by O2-O collision is studied in the temperature range 2000–7000K with physical kinetics and molecular collision dynamics. This study shows that all the potential energy surfaces appearing in the collision must be considered to correctly calculate rate constants, and that the Bethe-Teller theory is inadequate to describe vibrational relaxation in strong non-equilibrium, and validates widely used experimental models for vibrational relaxation.