Nitrogen fixation is industrially realized by mass production of ammonia, the principal intermediate nitrogen source for N-containing organic molecules. Instead, direct C-N bond formation from dinitrogen (N-2) is of great interest but remains a challenge. Here, by virtue of unique plasma-liquid interactions, we developed an environmentally benign one-pot approach to directly couple benzene and N-2, two naturally abundant yet chemically inert molecules, into value-added arylamines. Under the optimal conditions, an amination yield of 45 % was rapidly achieved, far better than the reported benzene amination efficiency using ammonia. A tentative reaction mechanism was proposed involving the long-lived N-2 (A(3)sigma u+ ) and N-2(+) species, as evidenced by the key intermediates detected. With a deeper mechanistic understanding and by further optimizing the plasma reactor, the realization of cost-effective electrical amination of benzene with N-2 could become reality.