Sm-Co rare earth permanent magnet materials are widely used in special fields such as new energy and electronic information. Sm-Co permanent magnet scraps are generated during the preparation and the use of end-of-life permanent magnets, which need to be recycled for the sustainable development. It is proposed to selectively recover Sm from the Sm-Co permanent magnet scraps by vacuum distillation. The experimental investigations were carried out in a vacuum furnace with double temperature zones for the efficient condensation of Sm vapor based on the thermodynamic and kinetic calculations. The recycling feasibility of the recovery of rare earth and the evaporation mechanism of Sm were also demonstrated in this work. The results show that Sm with the purity over 99% was obtained by the molybdenum condenser used as a condensing collectors at given conditions, providing a reference for the pyrometallurgical recovery of rare earth secondary resources.