Only one intermediate compound Ba3Lu4O9was identified at 1373, 1573 and 1773K in the BaO-Lu2O3system in present work.Based on the available experimental phase diagram and relevant thermodynamic data, BaO-Lu2O3 binary system was optimized and calculated by using CALPHAD method. The Gibbs free energy of high temperature solution was described by an ionic two-sublattice model as (Ba2+,Lu3+)P(O2-)Q. The calculated phase diagram, Gibbs energy of intermediate phase Ba3Lu4O9and Gibbs energy of mixingagreewell with experimental resultswithin error limits. The study will offer theoretical basis for further research of the phosphor matrix system of BaO-Lu2O3-SiO2, but also provide new idea for the phase diagram and thermodynamic research on related metallurgical slags, refractories, high-temperature superconductivity material systems.