Herein we report the demonstration of electrochemical deposition of silicon p-n junctions all in molten salt. The results show that a dense robust silicon thin film with embedded junction formation can be produced directly from inexpensive silicates/silicon oxide precursors by a two-step electrodeposition process. The fabricated silicon p-n junction exhibits clear diode rectification behavior and photovoltaic effects, indicating promise for application in low-cost silicon thin film solar cells.