In the moist environment of soil-water-air, there is a problem of low accuracy in monitoring volatile organic compounds (VOCs) using a photoionization detector (PID). This study is based on the PID water-soil-gas VOC online monitor developed by this group, online monitoring of the concentration of different constituents of VOCs in different production enterprises of the petroleum and chemical industries in Shandong Province, with the concentration of the laboratory test, to build a relevant model. The correlation coefficient about the PID test concentration and the actual concentration correlation coefficient was obtained through the collection of a large number of data trainings. Based on the application of PID in VOC monitoring, the establishment of a PID high-precision calibration model is important for the precise monitoring of VOCs. In this paper, multiple quantitative analyses were conducted, based on SVM regression of PID response to VOC signals, to study the high-precision VOC monitoring method. To select the response signals of PID under different concentrations of environmental VOCs measured by the research group, first, the PID response to VOC signals was modeled using the support vector machine principle to verify the effect of traditional SVM regression. For the problem of raw data redundancy, calculate the time-domain and frequency-domain characteristics of the PID signal, and conduct the principal component analysis of the time-domain of the PID signal. In order to make the SVM regression more generalized and robust, the selection of kernel function parameters and penalty factor of SVM is optimized by genetic algorithm. By comparing the accuracy of PID calibration models such as PID signal feature extraction, SVM regression, and principal component analysis SVM regression, the superiority of photoionization detector using the signal feature extraction PCA-GA-SVM method to monitor VOCs is verified.