Cryogenic separation method is the main method to recycle NGL (Natural Gas Liquid). Oilfield two-stage expansion NGL cryogenic separation plant is a complex system composed of varieties of material flow, energy flow and equipments, is a typical distributed energy use system composed of three parts, energy supply, energy use and waste heat recovery. In this paper, according to the process characteristics of two-stage expansion cryogenic separation plant, three-box analysis method was used, the system was compartmentalized into six subsystems, represented the exergy analysis model of system—unit—equipment, given the specific analysis process and the assessment rules for the NGL system. Using the practical operational data, the writers conduct the exergy analysis on the operational working condition of Daqing oilfield NGL system. Based on the calculation results, this paper raises some proposals to improve the operational efficiency, and achieved a good energy saving effect in engineering practice.