The invention relates to a continuous emission monitoring system for volatile organic compound pollutants in industrial flue gas, and belongs to the technical field of continuous emission monitoring of industrial flue gas. The system comprises five parts, namely, a sampling subsystem, a back flushing subsystem, a gas supply subsystem, a gas detection subsystem and a control subsystem, wherein the sampling subsystem is used for continuously sampling flue gas in a flue into a sample loop; the back flushing subsystem is used for cleaning a sampling probe; the gas supply subsystem is used for providing carrier gas for back flushing of the sampling probe and sample feeding and analysis of the detection subsystem; the gas detection subsystem is used for analyzing components and concentration of VOCs in sample gas on line; the control system is used for controlling running of the whole detection system and monitoring the concentration of VOCs in the flue gas on line. According to the system, the flue gas is continuously acquired and stored in the sample loop, and online sample feeding and detection of the sample gas is implemented through a six-way valve, so that sampling, detection, back flushing and a standby mode are switched; the system has the characteristics of being safe, reliable, highly accurate, low in replacement and maintenance cost, convenient to control and the like.