The separation of tantalum and niobium compounds has been of interest for many years, with few new developments. Classically separation is achieved by liquid–liquid extraction and most research focuses on optimising this process. A separation method that bypasses the need for liquid–liquid extraction is reported here. The process uses dry fluorination to convert tantalum and niobium pentoxides into metal oxyfluorides. The thermal behaviour of these species is sufficiently different for separation to be achieved by preferential volatilisation. Experimental results indicate that at least two temperature ranges are suitable for separation, viz. one below 165 °C, and one above 650 °C.