Electric field in nanosecond pulse discharges in ambient air is measured by picosecond four-wave mixing. Absolute calibration of the electric field is provided by the Laplacian field measured before breakdown, or by a separate measurement of a known electrostatic field. The measurements are done for two cases, (a) discharge between two parallel plate electrodes placed inside quartz sleeves, and (b) discharge between a razor edge electrode and distilled water surface. In the first case, breakdown field exceeds DC breakdown threshold by approximately a factor of two, 75 ± 7.5 kV/cm. The electric field follows the applied voltage before breakdown and decreases rapidly after breakdown, due to charge separation and plasma self-shielding. Sub-nanosecond time resolution (up to 0.2 ns) is obtained by monitoring the timing of individual laser shots relative to the voltage pulse, and post-processing four-wave mixing signal waveforms saved for each laser shot, placing them in the appropriate “time bins”. In the second case, electric field is measured for both positive and negative pulse polarities, with pulse durations of ~ 10 ns and ~ 100 ns, respectively. In the short duration, positive polarity pulse, breakdown occurs at 85 kV/cm, after which the electric field decreases over several ns due to charge separation in the plasma, with no field reversal detected when the applied voltage is reduced. In the long duration, negative polarity pulse, breakdown occurs at a lower electric field, 30 kV/cm, after which the field decays over several tens of ns and reverses direction when the applied voltage is reduced at the end of the pulse. For both pulse polarities, electric field after the pulse decays on a microsecond time scale, due to residual surface charge neutralization by transport of opposite polarity charges from the plasma. Measurements 1 mm away from the discharge center plane, ~ 100 μm from the water surface, show that during the voltage rise, horizontal field component (Ex) lags in time behind the vertical component (Ey). After breakdown, Ey is reduced to near zero and reverses direction. Further away from the water surface (≈ 0.9 mm), Ex is much higher compared to Ey during the entire voltage pulse. The results provide insight into air plasma kinetics and charge transport processes near plasma-liquid interface, over a wide range of time scales.