We studied the purification of metallurgical grade Si from solutions of K2SiF6 in fluoride melts using a molten salt electrorefining process at 700 °C. Electrorefining close to the deposition potential gave dense, coherent, and well-adherent deposits. It was shown that the deposition rate and microstructure of Si strongly depend on the process temperature. Deposited polycrystalline silicon has a well defined rod shape and crooked structure that varies with current density. The anodic dissolution rate is affected by the initial concentrations of K2SiF6 and the applied current density. The results of an inductively coupled plasma (ICP) analysis indicated that recovered silicon fiber deposits with purities greater than 99.98% can be obtained using the developed technique. The morphology of the electrodeposited silicon on silver substrates is discussed in the context of a cathodic reaction on the electrode surface, and a comprehensive explanation of the purification mechanism with salt removal is provided.