The development of the International Global Navigation Satellite System (GNSS) Service (IGS) Real-Time Pilot Project shows promise for real-time GNSS-based precipitable water vapor (GNSS-PWV) retrieval. For better applications of real-time GNSS meteorology over China, a method is proposed to establish a real-time GNSS-PWV monitoring system using the national GNSS network of China. The prototype system generating the zenith tropospheric delay (ZTD) is based on the real-time precise point positioning technique, in which the real-time data streams and state-space-representative satellite orbit and clock corrections are processed. The parallel computing technology is embedded in the system for decoding and processing the real-time data streams, which enables the multistation processing mode and improves the computing efficiency. At the initial phase, a total of 215 global positioning system (GPS) stations from the crustal movement observation network of China are used to generate the real-time GPS-ZTDs. The pressure data for separating the zenith wet delay (ZWD) from the ZTD are obtained from the collocated meteorological sensors. An advanced weighted mean temperature model, namely, Gridded-Mixed Tm , is adopted in the system to determine the conversion factor “Π” (converting GPS-ZWD to GPS-PWV) in real-time mode with the measured temperatures input. The generated real-time GPS-PWV products have a time resolution of 5 min. To validate the system performance, comparisons between the real-time GPS-PWV and the PWVs derived from nearby radiosonde data (RS-PWV) and reanalysis data from the National Centers for Environmental Prediction (NCEP)-Department of Energy Reanalysis II (NCEP-II-PWV) are conducted over a period of 83 days. The comparisons show a mean bias of −0.1 mm with a root mean square (RMS) of 1.7 mm between the real-time GPS-PWV and RS-PWV. The agreement between the real-time GPS-PWV and NCEP-II-PWV is approximately 2.0 mm in terms of RMS and has a mean bias of −0.8 mm. These results confirm that the established system can be used for real-time PWV monitoring across China.