It is very challenging to fabricate spherical refractory material powders for additive manufacturing (AM) because of their high melting points and complex compositions. In this study, a novel technique, freeze-dry pulsated orifice ejection method (FD-POEM), was developed to fabricate spherical MoSiBTiC particles without a melting process. Elemental nanopowders were dispersed in water to prepare a high-concentration slurry, which was subsequently extruded from an orifice by diaphragm vibration and frozen instantly in liquid nitrogen. After a freeze-drying process, spherical composite particles with arbitrary composition ratios were obtained. The FD-POEM particles had a narrow size range and uniform elemental distribution. Mesh structures were formed within the FD-POEM particles, which was attributed to the sublimation of ice crystals. Furthermore, owing to their spherical morphology, the FD-POEM particles had a low avalanche angle of 42.6°, exhibiting good flowability. Consequently, the combination of FD-POEM and additive manufacturing has great potential for developing complex refractory components used in industrial applications.