In the present work, spheroidization of angular vanadium powders using a radio frequency (RF) thermal plasma process is investigated. Initially, angular vanadium powders are spheroidized successfully at an average particle size of 100 μm using the RF-plasma process. It is difficult to avoid oxide layer formation on the surface of vanadium powder during the RF-plasma process. Titanium/vanadium/stainless steel functionally graded materials are manufactured with vanadium as the interlayer. Vanadium intermediate layers are deposited using both angular and spheroidized vanadium powders. Then, 17-4PH stainless steel is successfully deposited on the vanadium interlayer made from the angular powder. However, on the surface of the vanadium interlayer made from the spheroidized powder, delamination of 17-4PH occurs during deposition. The main cause of this phenomenon is presumed to be the high thickness of the vanadium interlayer and the relatively high level of surface oxidation of the interlayer.