In order to find a safe and controllable synthetic process of nitrogen trichloride, electrochemical oxidation of ammonium chloride solution and hydrochloric acid was researched. Carbon tetrachloride was added to extract the product in situ prior to electrochemical procedure. The structure of product was characterized by FT-IR and Raman. The main reaction conditions such as temperature and acidity of solution were observed. The optimum reation conditions are current 600 mA, reaction temperature 15 ℃, acidity of solution 2 mol·L^-1. The mass fraction of nitrogen trichloride is 10.1% for 6 h and the current efficiency is about 75%. The mass fraction of product after 7d dropped to 60% of initial value at 25 ℃.