During the steelmaking process, a great amount of slag is generated as a by-product. Vanadium-bearing steelmaking slags are classified as hazardous and require special handling and storage due to the toxicity of vanadium pentoxides. At the same time, such slags are valuable sources for the recovery of vanadium. The present work reviews the investigations on vanadium recovery from CaO-SiO2-FeO-V2O5 thin film slags under the neutral and oxidizing conditions in the temperature range 1653 K to 1693 K (1380 °C to 1420 °C) using Single Hot Thermocouple Technique (SHTT). The slag samples were analyzed by SEM/EDX. The results indicated that vanadium pentoxide evaporation can be up to 17.73% under an oxidizing atmosphere, while spinel formation under an argon atmosphere was detected in the conditions of thin film slags.