Sample pretreatment is one of the key steps in sample analysis. The design and development of new materials promote advancements in sample pretreatment technology. Deep eutectic solvents (DESs) are a novel material that have been developed in recent years. They possess characteristics such as low toxicity, good thermal stability, simple preparation methods, and low cost. DESs have the potential to replace traditional organic extraction solvents. DESs are formed from a hydrogen bond donor (HBD) and acceptor (HBA). Changing the type of HBA and HBD or their ratio leads to variations in the structure and properties of the resulting DESs. Gas chromatography (GC) and gas chromatography-mass spectrometry (GC-MS) are the primary analytical techniques used in laboratories. This paper analyzes the selection relationship between DESs and analytes, as well as the steps of sample pretreatment, based on the characteristics of GC instruments, and utilizing DES extractants and extraction materials for sample pretreatment. This paper summarizes the progress of DES-based microextraction methods for GC. It introduces the different classifications of liquid and solid-phase microextraction and the application of DESs in them. The theoretical mechanism and extraction/separation mechanism of DESs are analyzed, and potential application of DESs in extraction/separation technology is discussed.