The multifilter rotating shadowband radiometer (MFRSR) measures direct and diffuse irradiances in the visible and near-infrared spectral range. In addition to characteristics of atmospheric aerosols, MFRSR data also allow retrieval of precipitable water vapor (PWV) column amounts, which are determined from the direct normal irradiances in the 940-nm spectral channel. The HITRAN 2004 spectral database was used in our retrievals to model the water vapor absorption. We present a detailed error analysis describing the influence of uncertainties in instrument calibration and spectral response, as well as those in available spectral databases, on the retrieval results. The results of our PWV retrievals from the Southern Great Plains (SGP) site operated by the Department of Energy (DOE) Atmospheric Radiation Measurement (ARM) Program were compared with correlative standard measurements by microwave radiometers (MWRs) and a global positioning system (GPS) water vapor sensor, as well as with retrievals from other solar radiometers (AERONET's CIMEL, AATS-6). Some of these data are routinely available at the SGP's Central Facility; however, we also used measurements from a wider array of instrumentations deployed at this site during the water vapor intensive observation period (WVIOP2000) in September–October 2000. The WVIOP data show better agreement between different solar radiometers or between different microwave radiometers (both groups showing relative biases within 4%) than between these two groups of instruments, with MWR values being consistently higher (up to 14%) than those from solar instruments (especially in the large PWV column amount range). We also demonstrate the feasibility of using MFRSR network data for creation of 2D data sets comparable with that of the MODIS satellite water vapor product.