A method for isolating and purifying 1,1,1,2,2-pentafluoroethyl iodide or hydrogen fluoride from a mixture containing 1,1,1,2,2-pentafluoroethyl iodide and hydrogen fluoride, characterized by conducting liquid-liquid separation of a heterogeneous mixture containing 1,1,1,2,2-pentafluoroethyl iodide and hydrogen fluoride and distilling a layer of pentafluoroethyl iodide or a layer of hydrogen fluoride so that an azeotropic mixture of 1,1,1,2,2-pentafluoroethyl iodide and hydrogen fluoride is removed through the top of a distillation column while 1,1,1,2,2-pentafluoroethyl iodide or hydrogen fluoride is obtained from the bottom of the distillation column.