Recently, the development of a process to separate W and Co from tungsten carbide-cobalt (WC-Co) hard metal wastes has become important. In this study, we proposed a novel hydrometallurgical process involving the following steps: pretreatment, leaching, ion exchange, and two-step solvent extraction (I) and (II) using ionic liquids (lLs). First, an AICrN film coating was completely removed from a WC-Co hard metal sample by leaching in a H2SO4-H3PO4 mixed acid medium at 423 K for 120 h. Then, the sample was oxidized at 1173 K for 10 h and XRD analysis showed that WO3 and CoWO4 were generated during this oxidization. After the oxidization, the leaching reaction WO3 + 2LiOH -> WO42- + 2Li + H2O smoothly proceeded in leaching solution of 0.1 mol/L LiOH at 343 K for 19 h and the stoichiometry of WO3:LiOH was 1:2, which was consistent with that of the leaching reaction. Further, after the leaching step was completed, it was beneficial to exchange H+ and Li+ in the leaching solution using a cation exchange resin. Solvent extraction was performed using triethyl-n-pentyl phosphonium bis(trifluoromethylsulfonyl)amide as the IL, and tri-n-octylamine was employed as the extractant for the selective separation of W(VI) for solvent extraction (I). The extraction percentages (E) of W(VI) and Co(II) were >95% and <2.5% at pH=1.0, respectively, and the selective extraction of W(VI) was confirmed in this study. The extraction mechanism of W(VI) was based on the ion association reaction n[R3N](org) + [HxWyOzn-](aq)+n[H+](aq) double left right arrow [(R3NH)(n)HxWyOz](org). In solvent extraction (II), a PC-88A/[P-2225][NTf2] system was used for the effective extraction of Co(II) at pH>4.3. The slope analysis results showed that the extraction mechanism was governed by the cation exchange reaction [Co2+](aq)+2[(HL)(2)](org) double left right arrow [CoL2 center dot 2HL](org) + 2[H+](aq). A series of novel hydrometallurgical process using IL enabled us to demonstrate that W(VI) and Co(II) were efficiently recovered from WC-Co hard metal wastes.