Plasma catalysis has recently been recognized as a promising route for artificial N2 reduction under mild conditions. Here we report a highly active VN catalyst for plasma-catalytic NH3 synthesis via the typical Mars-van Krevelen (MvK) mechanism. Our results indicate that NH3 synthesis occurs through the continuous regeneration and elimination of nitrogen vacancies on the VN surface. With this strategy, the VN catalyst achieves a superhigh NH3 yield of 143.2 mg h-1 gcat.-1 and a competitive energy efficiency of 1.43 gNH3 kW h-1.