The industrial use of cryogenic air separation units started more than 120 years ago. Cryogenic air separation processes produce pure nitrogen, oxygen, and argon, as well as other noble gases. In cryogenic air separation units, the produced amounts of nitrogen and oxygen vary between 200 and 40,000 Nm 3 / h and 1000 and 150,000 Nm 3 / h , respectively. Different configurations of this process lead to various amounts of gaseous and liquid products. In addition, the purity of the products is affected by the schematic. Oxygen in gaseous or liquid form is typically used in the metallurgical (e.g., steel) industry, in chemical applications (as oxidizer), in power plants (for oxy-fuel combustion processes), as well as in the medical and aerospace sectors. Nitrogen in gaseous or liquid form is used as inert or flushing gas in the chemical industry and as a coolant for different applications. In this chapter, different schematics of air separation units are analyzed. An exergetic analysis is applied in order to identify the thermodynamic inefficiencies and the processes that cause them. Finally, the systems are evaluated from the economic point of view.