Surface pressure ( P s ) and weighted mean temperature ( T m ) are two necessary variables for the accurate retrieval of precipitable water vapor (PWV) from Global Navigation Satellite System (GNSS) zenith total delay (ZTD) estimates. The lack of P s or T m information is a concern for those GNSS sites that are not collocated with meteorological sensors. This paper investigates an alternative method of inferring accurate P s and T m at the GNSS station using nearby synoptic observations. P s and T m obtained at the nearby synoptic sites are interpolated onto the location of the GNSS station by performing both vertical and horizontal adjustments, in which the parameters involved in P s and T m calculation are estimated from ERA-Interim reanalysis profiles. In addition, we present a method of constructing high-quality PWV maps through vertical reduction and horizontal interpolation of the retrieved GNSS PWVs. To evaluate the performances of the P s and T m retrieval, and the PWV map construction, GNSS data collected from 58 stations of the Hunan GNSS network and synoptic observations from 20 nearby sites in 2015 were processed to extract the PWV so as to subsequently generate the PWV maps. The retrieved P s and T m and constructed PWV maps were assessed by the results derived from radiosonde and the ERA-Interim reanalysis. The results show that (1) accuracies of P s and T m derived by synoptic interpolation are within the range of 1.7–3.0 hPa and 2.5–3.0 K, respectively, which are much better than the GPT2w model; (2) the constructed PWV maps have good agreements with radiosonde and ERA-Interim reanalysis data with the overall accuracy being better than 3 mm; and (3) PWV maps can well reveal the moisture advection, transportation and convergence during heavy rainfall.