Since molybdenum has very high melting point of 2620 °C, there are many difficulties in its forming and post-processing, especially for deep processing. Furthermore as molybdenum is expensive, the utilization rate is important for the molybdenum processing. Additive manufacturing can directly manufacture the parts without mold and increase the utilization rate, and brings an opportunities for the new direction of deep processing for molybdenum. Due to the high quality requirements of molybdenum powder in additive manufacturing technology, the high-quality spherical molybdenum powder was prepared by plasma rotating electrode process method in the present study. The morphology, particle size and particle size distribution, chemical and physical properties were investigated. The molybdenum powder prepared by plasma rotating electrode process method showed to have high purity, high sphericity, good fluidity and high bulk density, proper particle size distribution and low gap element within the powder. The microstructure of the powder was a mixed structure of dendrites and cell crystals formed by rapid solidification, and as the particle size of the powder gradually decreased, the microstructure of the powder surface was remarkably refined. Within a certain range, the molybdenum powder with a wide particle size distribution had better fluidity and higher bulk density. The high-quality spherical molybdenum powder was prepared by plasma rotating electrode process method, which can meet the requirements of additive manufacturing technology for powder material performance.