Results of theoretical and experimental studies of the physicochemical properties of slags of the CaO–SiO2–B2O3 system containing 15% Al2O3 and 8% MgO lie at the basis for the development of technology for exhaustive desulfurization of metal beneath basic boron-containing slags formed in a steelpouring ladle in a ladle-furnace unit (LFU), and steel direct microalloying with boron. Methods of simplex lattice planning of an experiment, a software complex HSC 6.1 Chemistry (Outokumpu), and the method of electro-vibration viscosimetry are used. Results of thermodynamic modeling of the effect of slag basicity and B2O3 content on sulfur and boron equilibrium distribution coefficient between slag of the oxide system under study and low-carbon metal are presented. The quantitative effect of basicity and B2O3 content on slag viscosity containing 15% Al2O3 and 8% MgO at a temperature of 1600°C and the influence of the slag chemical composition of the oxide system under study on the degree of wear of periclase-carbon refractory material are shown. Results of studying physicochemical properties of slags of the CaO–SiO2–B2O3 system containing 15% Al2O3 and 8% MgO are a basis for developing a ladle slag composition with low viscosity and providing exhaustive metal desulfurization, and direct microalloying of boron steel with low corrosive effect on periclase-carbon refractories. Development of this technology provides, depending on the steel grade, a boron content of 0.001–0.008%, low metal sulfur concentration at 0.004–0.014%, a reduction in manganese ferroalloy consumption from 0.5 kg/ton of steel 08KP to 1.4 kg/ton of steel 09G2S, exclusion of ferroboron and fluorspar additives in the ladle, and achievement of good finished metal product mechanical properties.