In this study, simple and a rapid solvent extraction method is investigated to recover Mo(VI) from simulated HLLW. The (NH₄)₆Mo₇O₂₄·4H₂O dissolved in 3 M HNO₃ was treated with ascorbic acid and KSCN to form orange red colored Mo(V)-SCN. Reduction of Mo(VI) was confirmed by cyclic voltammetry. The freshly formed complex was completely extracted to ethyl acetate layer. The organic solvent could be recovered using rotary evaporator. The Mo-complex disproportionated gradually to form a yellow solid, Mo(OH)₂(SCN)_3·6H₂O, which forms MoO₃ @ 400°C. The solid product was characterized by XRD, FT-IR, EDX, TG–DSC and SQUID measurements.