Abstract: The spherical Ti–10V–2Fe–3Al alloy (TB6) powders were prepared by the plasma rotating electrode processing (PREP), using the raw materials of TB6 rods. The influence of titanium alloy electrode rotational speed on the particle size and shape of spherical powders was studied, the variation patterns between powder particle size and the content of O and N, along with the phase composition, were systematically analyzed. The experiment indicates that the higher the electrode rotational speed, the broader the particle size distribution range of the alloy powders, with a higher proportion of smaller particle size powders and a smaller average particle size powders. The particle size distribution range of the powders is 70～170 μm at a rotation speed of 20,000 r/min, and respectively, the particle size distribution range is 40～160 μm at a rotation speed of 28,000 r/min. The smaller the particle size of the TB6 powders, the less cellular dendritic structure, and the more O and N elements are adsorbed on the powders surface with the smoother spherical powders surface. The powders produced at a rotation speed of 28,000 r/min are predominantly composed of β-Ti phase, with minor α-Fe phase. The powders prepared by the PREP method show excellent sphericity with minimal satellite particles, and are suitable for Selective Laser Melting.