Pure rotational CARS thermometry, complemented by UV emission measurements and ICCD imaging, is used to study kinetics of low temperature plasma assisted fuel oxidation and ignition in a repetitive nanosecond pulse discharge in hydrogen–air mixtures, with number of pulses in a 40kHz burst varying from a few to a few hundred. Time-resolved OH emission, coupled with gated ICCD images of the plasma and the flame, demonstrate that volumetric ignition of H₂–air mixtures occurs in a spatially uniform plasma. The results are shown to agree well with predictions of a new hydrogen–air plasma chemistry model, which incorporates non-equilibrium plasma processes, H₂–air chemistry, non-empirical scaling of nanosecond pulse energy coupled to the plasma, and quasi-one-dimensional conduction heat transfer. In particular, the results demonstrate that the heating rate in low temperature hydrogen–air plasmas is much faster than in air plasmas, primarily due to energy release from exothermic reactions of fuel with O and H atoms generated in the plasma. Kinetic sensitivity analysis is used to identify dominant plasma and chemical processes of hydrogen oxidation, demonstrating that additional heat release in these reactions is a key factor in ignition kinetics. Kinetic modeling calculations demonstrate that removal of the radical generation processes by the nanosecond pulsed plasma from the model completely blocks subsequent exothermic chemical reactions, thus making ignition impossible.