A large amount of bischofite is produced in the process of potassium extraction from salt lake, which seriously affects the ionic balance of brine system. In this study, a high-purity magnesia spinel refractory raw material with a spinel-wrapped periclase structure was directly prepared using bischofite by a precipitation-sintering approach. A coupling process of one-time crude magnesium chloride solution recrystallization and three-time precipitates washing was employed to remove crucial impurities (sodium, potassium, boron, etc.) and prepare the magnesium hydroxide precipitates with a high purity of 99.37 %. The lightly calcined magnesia gained from the high-purity magnesium hydroxide precipitates and white corundum were then employed for preparing the refractory raw materials. The effects of particle size and dosage of white corundum on the phase distribution, microstructure, and physical properties of the materials were thoroughly studied. The results illustrated that the prepared refractory raw materials were mainly composed of periclase and spinel phases, showing a distinct spinel-wrapped periclase structure that could enhance the physical properties. Therefore, the prepared refractory raw materials showed a high bulk density of 3.46 g·cm−3, a low apparent porosity of 2.46 %, and a linear shrinkage rate of 12.33 %, under the optimum conditions of white corundum particle size of 3.00 μm and alumina/magnesia mass ratio of 3:10.