Low-temperature plasma technology is a promising technological route to achieve green and efficient ammonia synthesis at ambient temperature and pressure. In this work, a Laval nozzle type gliding arc plasma reactor was designed for the direct synthesis of ammonia from N2 and H2 discharges ignited by a high voltage nanosecond pulsed power supply to investigate the effect of different electrode gaps, pulse voltages, and V N2:V H2 on ammonia synthesis. The nanosecond pulsed plasma discharges were characterized through oscilloscope and optical emission spectroscopy (OES). The maximum rate of NH3 synthesis was 538.12 μmol·h−1 at 1.5 mm electrode gap, 16 kV peak pulse voltage, 6 kHz pulse repetition frequency, 100 ns pulse width, 100 ns pulse rising edge, 100 ns pulse falling edge, and 200 mL·min−1 total gas flow rate with V N2:V H2 = 1:1. It was demonstrated that the discharge mode of the nanosecond pulsed gliding arc plasma can transit from a unipolar state to a bipolar state determined by the duty cycle accompanied with higher discharge power and vibrational temperature. Bipolar discharge mode is beneficial to improve the efficiency of plasma ammonia synthesis because of it can strengthen the plasma discharge and increase the vibrational temperature. The ammonia synthesis rate and N2 conversion rate increased with the increase of the discharge power and vibrational temperature.