The spatio-temporal rovibrational excitation and relaxation mechanisms of N2(X) in the post-discharge of a 10 ns high-voltage diffuse discharge are studied by spontaneous Raman scattering (SRS). It is shown that the vibrational excitation of nitrogen molecules remains high despite the strong electric fields applied during the discharge itself and the relaxation processes are similar to lower voltage ns discharges. The main differences with the lower field discharges are rather visible at the beginning of the discharge with a specific spatial volume distribution and a significant vibrational non-equilibrium between v = 0, 1 and v > 1. The spatial distribution of the rovibrational excitation of the diffuse discharge is very wide radially, consistent with the sustainability of fields greater than 100 Td over nearly 8 mm during propagation. The initial rovibrational excitation is inhomogeneous along the axis. The gas temperature reaches up to about 1200 K close to the pin (85 kV, ambient air) while it remains below 500 K in the rest of the volume. It is possible to control the heating of the discharge without greatly modifying the energy transfer mechanisms by adjusting the duration of the voltage pulse. In terms of reactivity, high atomic oxygen densities seem to be very localized in the vicinity of the pin (1024 m−3 at 1.5 mm from the pin, corresponding to about 20% dissociation). This inhomogeneity reflects the distribution of energy in the volume of the discharge. The main effects of humidity are also studied. It amplifies the fast heating and accelerates the decay of atomic oxygen in the post-discharge. No significant acceleration of the V–T relaxation of nitrogen due to the addition of water vapour was observed for the studied conditions. A shock wave was identified which is triggered at around 500 ns.