Sulfur hexafluoride (SF6) is an industrial gas used in various applications such as high-voltage electrical transmission and distribution systems, film protection, semiconductors, and plasma-etching processes. Compared with CO2, the most common greenhouse gas that has received a tremendous amount of attention, SF6 possesses a considerably higher potential for global warming and longer atmospheric lifetime. Conventional SF6 capture and recovery methods such as distillation and liquefaction are known to be costly due to the energy required for phase changes. The use of adsorbents and membranes in SF6 separation has therefore been extensively studied for its attractive advantages such as lower energy penalty. In this review, we present a brief overview of the current status of SF6 separation based on adsorbents and membranes together with the technical challenges involved in such separation processes for potential industrial applications.