Ladle furnace slag (LFS) shows excellent potential for valorization. Despite this, landfills are typically its final destination, mainly because of technological barriers in its valorization process. This work examines the potential use of LFS as a partial cement/fine aggregate replacement, focusing on the effects of LFS composition and particle size distribution on concrete physico–mechanical properties. Chemical/mineralogical characterization of raw/hydrated samples, fresh-/hardened-state concrete properties, and volumetric instability tests were evaluated. Our results show reduced mechanical performance with LFS replacement, reaching compressive strength values of 32–42 MPa after 28 days. LFS mineralogical characterization reveals the absence of free CaO and the presence of periclase with its hydration/carbonation products. Therefore, the weathering/maturity process mainly affects free CaO. Furthermore, the observed volumetric instability issues were within the Code on Structural Concrete (Spanish abbreviation: EHE) established limits (0.04%), suggesting that the remaining periclase could be responsible for this expansive behavior.