Precipitable water vapor (PWV) is a vitally important factor in atmospheric circulation. PWV is significant for forecasting extreme weather and understanding the dynamics of climate change. Comprehensively evaluating the performance of newly proposed remotely sensed water vapor products is crucial for guaranteeing their suitability for futural PWV applications. In this study, the accuracy of the recently established remotely sensed water vapor product from the Visible Infrared Imaging Radiometer Suite (VIIRS) satellite sensor on the Suomi National Polar-orbiting Partnership (SNPP) (VIIRS-PWV) platform within various regions of mainland China was evaluated via the PWV from Global Positioning System (GPS) observations. The GPS-derived PWV from 231 stations of the Crustal Movement Observation Network of China (CMONOC) from 2012 to 2018 was obtained through precise point positioning (PPP) techniques. The results showed that the mean value of the correlation coefficient (CC), the mean bias (MB), and the root-mean-square error (RMSE) between the VIIRS-PWV and the GPS-PWV were 0.92, −1.6 mm, and 4.7 mm, respectively. These values were comparable with the results of the PWV data derived from the Atmospheric Infrared Sounder (AIRS) and Moderate Resolution Imaging Spectroradiometer (MODIS) products. This indicates that the VIIRS product could provide PWV data with satisfactory accuracy for large-area scientific applications. Moreover, the MB and RMSE of the differences between the GPS-PWV and VIIRS-PWV showed obvious seasonal variations. The VIIRS-PWV generally performed better in winter (with the MB and RMSE values of 0.1 mm and 2.3 mm) than in summer (with the MB and RMSE values of −4.4 and 7.0 mm). Analysis among different regions revealed that the Central South (CS) region of China attained the largest mean RMSE value of 6.3 mm, and the North West (NW) region attained the smallest mean RMSE value of 3.8 mm. In addition, the southern region of China obtained a mean RMSE value of 5.6 mm, while that for the northern region of China was 3.9 mm. This indicates that the VIIRS-PWV has better accuracy within the northern region of China than within the southern region.