Molten salt electrolysis has been widely used in the production and separation of metals, but it still lacks in situ real-time analysis methods to monitor the electrolysis process. In this work, a microplasma spectroscopic real-time analysis (MIPECA) system is developed based on noncontact direct current (DC) glow discharge. With the MIPECA system, the atomic emission spectroscopy of Li and K could be obtained in situ in LiCl-KCl molten salt, and the impact of different operating conditions on spectral signals was investigated. Then, the characteristic spectra of ten representative elements, including alkali metals (Na, Cs), alkaline earth metals (Mg, Ca, Sr, Ba), transition metals (Ag, Cu, Ni), and lanthanide metals (Ce), were all successfully excited for qualitative analysis. Under the optimal operating conditions, quantitative analysis of Ag, Cs, and Sr was achieved with high sensitivity and low limits of detection (LOD) of about 0.063, 0.021, and 0.073 wt %, respectively. Finally, the electrolysis process of Ag+ in LiCl-KCl molten salt was real-time monitored by using this MIPECA system, showing its application potential in molten salt electrolysis.