Basic-oxygen furnace (BOF) slag is the second abundant by-product from the steel-making process. It is not readily recycled for high phosphorus content and volume instability. To eliminate its phosphorus-hosting dicalcium silicate (C2S) and volumetrically unstable free-lime, reductive heating experiments on BOF-slag are carried out at 1300-1600 degrees C using quartz-sand or serpentine as a basicity modifier. In the products, C2S and free-lime are consumed through reacting with CaO and MgO, which are produced by Ca-ferrite and Mg-wustite reduction, respectively, to formmerwinite and akermanite. The products are also characterized by silicatemetal segregation and the extent of that increases with increasing temperature and decreasing particle size of starting mixtures. Thermodynamic calculations show that phosphorus in C2S is mostly converted to Fe2P in the metal domain. Compared to the slag-serpentine experiments, the slag-quartz experiments resulted in higher extents of silicate-metal segregation with lower phosphorus contents of approximate to 0.1% in the silicate domain, which therefore is recyclable. To optimize silicate-metal segregation for recycling BOF-slag, it is suggested (i) bringing the BOF-slag composition within the low-temperature side of the C2S-merwinite-akermanite Alkemade triangle by adding quartz-sand; (ii) reductively heating to 1500-1600 degrees C; and (iii) cooling slowly then quenching to suppress C2S crystallization from melts.