At present, around 25% of water desalination processes are based on distillation. Similar to classical distillation, membrane distillation is a phased-change process in which a hydrophobic membrane separates two phases. Membrane distillation is considered an emerging player in the desalination, food processing and water treatment market. Due to its high salt rejection, less fouling propensity, operating at moderate temperature and pressure, membrane distillation is considered as a future sustainable desalination technology. The distillation process is quite well known in desalination. However, membrane distillation emerged a few decades ago, and a thorough understanding is needed to adapt this technique in the near future. This review chapter introduces the classical distillation and membrane distillation as an emerging technology in the desalination arena. Heat and mass transfer and thermodynamics in membrane distillation, characteristics of the performance metrics of membrane distillation are also described. Finally, the performance evaluation of MD is presented. The possibility of using low-grade heat in membrane distillation allows it to integrate directly to solar energy and industrial waste heat.