An integrated experimental and thermodynamic modelling study of the phase equilibria in the FeOFeO1.5- SbO1.5-SiO2 system in equilibrium with liquid Sb and Sb-Ag metal has been undertaken to develop thermodynamic model of the Na-Si-Fe-O slag system with S-Sn-Sb-Pb-As minor elements based on the experimental investigation of the selected sub-systems. New experimental phase equilibria data at 575–1600°C were obtained for this system using high-temperature equilibration of synthetic mixtures with predetermined compositions in sealed silica ampoules, Fe3O4 basket in sealed silica ampoule, or Re foils, a rapid quenching technique, and electron probe X-ray microanalysis of the equilibrated phase compositions. Experimental results on phase equilibria in the Fe-Sb-Si-O+Sb metal system obtained helped to produce initial set of model parameters in the slag. The primary phase fields of quartz/tridymite/cristobalite (SiO2), 2 high-SiO2 immiscible liquids, olivine (Fe2SiO4), wustite (FeO1+x), spinel (Fe3O4), schafarzikite (FeSb2O4) and valentinite/ senarmontite (Sb2O3) were identified in the binary Sb2O3-FeO, Sb2O3-SiO2 and ternary FeO-Sb2O3- SiO2 systems. Further refinement, particularly the distribution of excess Gibbs energy among the ‘FeO’-Sb2O3-SiO2 and ‘FeO1.5’-Sb2O3-SiO2 interactions, required the study at more oxidising conditions. Oxygen potential was increased using an inert metal (Ag) rather than using the gas flow due to the high volatility of Sb-containing gaseous species. Liquid Ag-Sb alloys with low concentrations of Sb of a few percent were used. At these conditions, the concentration of AgO0.5 in slag was below 1 mol per cent, which had a small effect on observed phase equilibria in the system. In addition, important information on the solubility of silver in slags is produced, which can be valuable when treating electronic recycling materials or primary silver-containing ores through the Pb process. Two main areas were addressed: the spinel-tridymite boundary (40–70 per cent SiO2 in slag) and spinel liquidus near 15 per cent SiO2 in slag. This allowed to deconvolute the separate contributions of the FeO-Sb2O3(-SiO2) and Fe2O3-Sb2O3(-SiO2) systems.