With the development of industrialization, fine particulate matter (PM2.5) severely chills the health of people. Studies have shown that the variation of PM2.5 concentration is related to the Global Navigation Satellite System (GNSS) tropospheric delay. Therefore, it is possible to use the widely distributed continuous operation reference station (CORS) to monitor and predict PM2.5 concentrations with high time resolution. In this paper, the zenith wet delay (ZWD) of five CORS located in Baoding, Hebei Province, China, from Sep 2014 to Feb 2015, is calculated firstly. Then, the correlation between PM2.5 and ZWD is investigated. Finally, the experimental data including PM2.5, ZWD, temperature, air pressure, and relative humidity data sampled in one hour are used to establish PM2.5 concentrations online prediction model based on support vector machine regression (SVMR) model with metabolic method. The experimental results show that in autumn and winter, the correlation coefficient between daily-mean PM2.5 and ZWD is mainly larger than 0.4, and the correlation coefficient between hourly mean PM2.5 and ZWD is mainly larger than 0.3. Meanwhile, in daily cycle analysis, air temperature, air pressure and relative humidity are related to PM2.5 concentration. Finally, Using SVMR model with metabolic method, by combining GNSS and meteorological factors, ideal short-term prediction accuracy is achieved, which shows that the use of GNSS and meteorological factors is potential in predicting PM2.5 concentration.