^81,82mRb and trace amount ^44mSc were produced by irradiation of potassium bromide target with 36 MeV alpha particle beam via ^natBr(α,xn)^81,82mRb and ⁴¹K(α,n)^44mSc reactions respectively. Different liquid–liquid extraction (LLX) studies were performed to determine best separation condition for Rb and Sc. In LLX (1) cation exchanger di-(2-ethylhexyl)phosphoric acid (HDEHP) dissolved in cyclohexane, (2) 18-crown-6 in nitrobenzene were used as organic phase and various concentration of HCl, HNO₃ and HClO₄ were used as aqueous phase. Radiochemical separation with high separation factor has been achieved.