A green route of electrochemical ammonia synthesis was realized for the first time by using doped LaFeO3 perovskite as an electrocatalyst under mild conditions. The NH3 formation rate of 13.46 mu g(NH3) h(-1) mg(cat)(-1) (3.52 X 10(-10) mol s(-1) cm(-2)) was achieved with the cell voltage of 2.4 V, and a faradaic efficiency of 1.99% was obtained when a cell voltage of 1.8 V was applied. The electrochemical ammonia synthesis was based on the chemisorption of N-2 molecules on oxygen vacancies in perovskites and the subsequent electrochemical hydrogenation.