Currently, Electric Arc Furnace Slag (EAFS) is undervalued and is therefore only used in road construction, while blast furnace slag (BFS) is used as an interesting alternative in construction materials to replace natural aggregates in the manufacture of concrete. Steel slag (SS) represents a promising secondary resource due to its high content of critical metals, such as chromium (Cr) and vanadium (V). These metals are essential for various strategic industries, making it crucial to consider slag as a resource rather than waste. However, the primary challenge lies in selectively recovering these valuable metals. In this work, we explore the development of a hydrometallurgical process aimed at efficiently extracting Cr and V from Electric Arc Furnace Slag (EAFS). The characterization of the investigated EAFS shows that the main crystalline phases contained in this heterogeneous material are srebrodolskite, larnite, hematite, and spinel such as probably magnesio-chromite. The targeted metals seem to be dispersed in various mineral species contained in the SS. An innovative hydrometallurgical method has been explored, involving physical preparation by co-grinding slag with alkaline reagents followed by treatment in a microwave furnace to modify the metal-bearing species to facilitate metal processing dissolution. The results obtained showed that the leaching rates of Cr and V were, respectively, 100% and 65% after 15 min of treatment in the microwave furnace, while, after 2 h of conventional heat treatment, as explored in a previous study, 98% and 63% of the Cr and V were, respectively, leached.