To make electrical energy from photovoltaic (PV) silicon (Si) solar cells competitive, the cost in each of the PV manufacturing process steps has to be diminished. Today, high-purity Si is produced by an energy-intensive process exhibiting high irreversible thermodynamic losses. The purity of the product from this process (99,9999999 pct [9 N]) far exceeds what generally is accepted to be the requirements for PV purposes (4 to 6 N). Here we show a novel method for the purification of Si based on the principle of electrochemical refining in a molten high-melting-point fluoride electrolyte at temperatures above the melting point of silicon 1685 K (1412 A degrees C). The method comprised a vertical stack of three molten layers with a metal alloy at the bottom, an intermediate electrolyte layer, and purified metal at the top. The integrity of the layers being secured was through the immiscibility of the liquids and the careful tailoring of the individual densities. Boron (B), exhibiting similar thermodynamic properties to Si, effectively was not removed. A suitable low-B feedstock may be identified in kerf from the sawing of mono- or multicrystalline Si blocks into wafers. To produce purified metal in the 6 N range, practice from electrorefining of aluminum shows that long-term, stable operation in large-scale industrial reactors is needed. The trends and mechanisms observed in the laboratory scale indicate that high purity also can be achieved for Si provided that these criteria can be met.