Zirconium(Zr) alloys are commonly used in the nuclear industry for applications such as fuel cladding and pressure tubes. To minimize the levels and volumes of radioactive waste, molten salts have been employed for decontaminating Zr alloys. Recently, a two-step Zr metal recovery process, combining electrolysis and thermal decomposition, has been proposed. In the electrolysis process, potentiostatic electrorefining is utilized to control the chemical form of electrodeposits(ZrCl). Although Zr metals are expected to dissolve into molten salts, reductive alloy elements can also be co-dissolved and deposited on the cathode. Therefore, a better understanding of the anodic side’s response during potentiostatic electrorefining is necessary to ensure the purity of recovered Zr and long-term process operation. As the first step, potentiodynamic polarization curves were obtained using Zr, Nb, and Zr-Nb alloy to investigate the anodic dissolution behavior in the molten salts. Nb, which has a redox potential close to Zr, and Zr exhibit active or passivation dissolution mechanisms depending on the potential range. It was confirmed that Zr-Nb alloy also has a passivation region between -0.223 to -0.092 V influenced by the major elements Zr and Nb. Secondly, active dissolution of Zr-Nb was performed in the range of -0.9 to -0.6 V. The dissolution mechanism can be explained by percolation theory, which is consistent with the observed microstructure of the alloy. Thirdly, passivation dissolution of Zr, Nb, and Zr-Nb alloy was investigated to identify the pure passivation products and additional products in the Zr-Nb alloy case. K2ZrCl6 and K3NbCl6 were identified as the pure passivation products of the major elements. In the Zr-Nb alloy case, additional products, such as Nb and NbZr, produced by the redox reaction of nanoparticles in the high viscous salt layer near the anode, were also confirmed. The anodic dissolution mechanism of Zr-Nb alloy can be summarized as follows. During active dissolution, only Zr metal dissolves into molten salts by percolation. Above the solubility near the anode, passivation products begin to form. The anode potential increases due to the disturbance of passivation products on ion flow, leading to co-dissolution of Nb. When the concentration of Nb ion exceeds the solubility, a passivation product of Nb also forms. In this scenario, a high viscous salt layer is formed, which traps nanoparticles of Zr metal, resulting in redox behavior between Zr metal and Nb ion. Some nanoparticles of Zr and Nb metal are also present in the form of NbZr.