Sensing of precipitable water vapor (PWV) using the Global Positioning System (GPS) has been intensively investigated in the past 2 decades. However, it still remains a challenging task at a high temporal resolution and in the real-time mode. In this study the accuracy of real-time zenith total delay (ZTD) and PWV using the GPS precise point positioning (PPP) technique is investigated. GPS observations in a 1 month period from 20 globally distributed stations are selected for testing. The derived real-time ZTDs at most stations agree well with the tropospheric products from the International Global Navigation Satellite Systems Service, and the root-mean-square errors (RMSEs) are <13 mm, which meet the threshold value of 15 mm if ZTDs are input to numerical weather prediction models. The RMSE of the retrieved PWVs in comparison with the radiosonde-derived values are ≤3 mm, which is the threshold RMSE of PWVs as inputs to weather nowcasting. The theoretical accuracy of PWVs is also discussed, and 3 mm quality of PWVs is proved achievable in different temperature and humidity conditions. This implies that the real-time GPS PPP technique can be complementary to current atmospheric sounding systems, especially for nowcasting of extreme weather due to its real-time, all-day, and all-weather capabilities and high temporal resolutions.