In order to develop a selective recovery process of tantalum and niobium from tungsten and cobalt extracted residue (WCR), the release of rare metals during chlorination in a chlorine stream in a fixed bed reactor was investigated. The chemical forms of niobium in the sample were estimated to be CrNbO(4) and (Ti, Nb, Fe, Ta) O(2). During chlorination at 573-1273 K, release of tantalum reached 15-46%, and that of niobium 74-97%. In the presence of added carbon, niobium originating from CrNbO(4) was released in the temperature range of 273-773 K, and niobium and tantalum originating from (Ti, Nb, Fe, Ta) O(2) were rapidly released into the gas phase at above 773 K. The carbochlorination enabled all niobium and tantalum in the solid phase to be released at the temperature of 873 K by changing their chemical forms to chlorides via oxychlorides. Two-step chlorination consisting of chlorination and carbochlorination was carried out for selective separation of niobium and tantalum from coexisting elements. During chlorination in the first step, 96% of niobium and 26% of tantalum were recovered from WCR. All of the tantalum in the residue of the first step could be released into the gas phase by addition of carbon, and a volatile composed of 80% of tantalum was obtained in the second step.