<p>This study investigated the effects of the melting process, crystallization kinetics, and structure of crystalline products in CaF₂-containing electroslag melting. Simultaneous thermal analysis, scanning electron microscopy-energy spectroscopy, and X-ray diffraction were used to analyze ZrO₂ contents of 0, 2 mass%, 4 mass%, 6 mass%, and 8 mass%. The results showed that as the content of ZrO₂ increased, the melting temperature and melting heat of the slag gradually increased. The CCT curve indicates that the initial crystallization temperature of the slag decreases and then increases. The crystallization ability of the slag gradually increased with an increase in ZrO₂ content from 0 mass% to 4 mass%. The main crystalline phases observed were elongated Ca₁₂Al₁₄O₃₂F₂, granular CaF₂, and irregular CaZrTi₂O₇.The crystallization ability of the slag gradually decreased as the ZrO₂ content increased from 4 mass% to 8 mass%. The main crystalline phase transformed into irregular Ca₁₂Al₁₄O₃₂F₂ and CaF₂, bone-like CaZrO₃, and dendritic MgO. The lowest activation energy of crystallization and the strongest crystallization ability were obtained by kinetic calculation when the content of ZrO₂ in the slag was 4%.</p>