The temporal dynamics of atmospheric-pressure nanosecond pulsed plasma discharges in a pin-to-pin electrode configuration are studied using streak-camera line imaging of the interelectrode gap with a time resolution as short as ∼25 ps. Discharge emission initiates homogeneously throughout the interelectrode gap with no detectable streamer propagation and then temporally decays in two distinct phases. Plasma emission bands attributed to various electronic transitions are tracked for single discharges in air and N2. Spectral filtering of the excited molecular states reveals that the N2(C–B) and N2(B–A) emission bands evolve in distinct early and late phases, respectively, with a time separation of ∼15–20 ns. Furthermore, significant differences in the temporal dynamics of plasma discharges in air and N2 are observed. High levels of excited-state atomic oxygen and NO appear after the initial decay of the N2(C) state and coincide primarily with the latter phases of plasma evolution in air environments. From temporal traces of discharge emission, the formation and relaxation timescales of the electronically excited states of N2 are quantified in pure N2 and air environments with sub-nanosecond resolution. The streak-OES (optical emission spectroscopy) technique enables quantitative time-resolved studies of key chemical species for model validation in ultra-short-pulsed plasmas.