Considering the requirement for a reduction of refractory consumption, the present work investigated the fabrication of Al2O3-MgO-CaO-based refractory with BaO addition by means of solid-state reaction sintering. The effect of BaO addition on densification and the properties of the refractory were also discussed. Results indicated that the formation of calcium hexaluminate (CaO·6Al2O3, or CA6) grains with a high aspect ratio in the alumina-rich zone depressed the densification of the sample without BaO addition, resulting in a higher apparent porosity of 21.2%. When 6 wt. % BaO was added, a new phase of Ba2Mg6Al28O50 (BAM) with a lower aspect ratio was formed and the densification of the sample with an apparent porosity of 5.52% was promoted. In addition, mechanical performance was significantly improved due to an increase in compactness and modification of the microstructure. The cold compressive strength increased from 348 MPa to 569 MPa and the flexural strength increased from 178 MPa to 243 MPa by addition of 6 wt. % BaO. Meanwhile, the breadth of the widest crack after the thermal shock test decreased from 7 μm to 1 μm in the refractory.