Electrocatalysis is an environmentally friendly synthesis method that overcomes thermodynamic limitations and enables some reactions usually requiring high temperature and high pressure to be realized under ambient conditions. The one-step electrochemical synthesis of ammonia and acetone under ambient conditions was realized using an Fe-modified graphite rod or an Fe-modified stainless steel mesh as the working electrode, nano-Fe as the catalyst, N2 and isopropanol as the raw materials, and an ionic liquid (a trihexyl tetradecyl phosphine hexafluorophosphate; [P6,6,6,14][F6P]) as the electrolyte. The NH3 yield, faradaic efficiency, and acetone yield were 103.6 mg m−2 h−1, 20%, and 1060.4 mg m−2 h−1, respectively, for the Fe-modified graphite rod and 56.0 mg m−2 h−1, 60%, and 573.2 mg m−2 h−1, respectively, for the Fe-modified stainless steel mesh. This is a “green” and clean synthesis of ammonia that provides a new method to synthesize economic products from inexpensive nitrogen.