Polysilicon is used as a raw material for photovoltaic devices, and has received a lot of attention to reducing production costs and simplifying processes. This research analyzed the electrochemical redox of silicon species SiO₂ and silicate(CaSiO₃) in 850℃ CaCl₂ molten salt, and observed the shape by electrodeposited silicon with the electrochemical reduction. Cyclicvoltammetry(CV) analysis was conducted in glassy carbon and Si wafer, and electrodeposition was conducted in Si wafer. In the CaCl₂ molten salt, it was confirmed that silicon was passivation due to the oxidation of silicon to Si-Cl and the low solubility of SiCl₄. It may be seen that in the CaCl₂ molten salt to which silicate was added, the reduction current was related to the diffusion of dissolved silicate. In the CaCl₂ molten salt to which SiO₂ was added, characteristics similar to the addition of silicate were observed, but the current was not large. In silicon electrodeposition, the shape according to the concentration and potential of the silicon precursor was confirmed.