The Atmospheric Infrared Sounder (AIRS) is the first of a series of satellite sensors that exploit high spectral resolution and broad spectral coverage of the midinfrared to improve the retrieval accuracy of passive infrared sounding. The AIRS atmospheric retrieval goals are to obtain 1 K accuracy for 1 km layers below 100 mb for temperature and 10% for 2 km layers for water vapor in clear and most cloud conditions. The AIRS total column precipitable water vapor (PWV) is obtained by integrating the vertical profile of water vapor mixing ratio derived from cloud-cleared radiances. The accuracy goal of the AIRS PWV product is 5%. This paper provides a validation of the AIRS PWV product at three distinct climate sites over the nearly full range of total water amounts observed on Earth (between 0.1 and 6.5 cm). Six years (September 2002 to August 2008) of AIRS v5 retrievals of PWV are evaluated against ground-based microwave radiometer (MWR) data at three Department of Energy Atmospheric Radiation Measurement program (ARM) sites. The accuracy of the MWR PWV retrieval is estimated to be between 1% and 3%. This study shows that the agreement between the MWR and AIRS retrievals of PWV is within 5% at all three ARM climate sites for most conditions. The notable exceptions are (1) very dry cases (PWV < 1 cm) over the Southern Great Plains (SGP) land site during both daytime and nighttime, where AIRS is too moist by 15%–30% and (2) nighttime observations over the SGP land site for PWV > 1 cm, where AIRS is too dry by about 10%. The moist bias for low water amounts (usually observed during the winter) over land could be a surface emissivity–related error since very little bias is seen at the ARM Arctic site for similar water amounts. The cause of the dry bias at nighttime over land for moderate water amounts is not determined by this study. However, a spatial map of the diurnal bias in monthly AIRS water amount suggests that this effect is related to meteorological conditions in the U. S. Great Plains, which in the summertime is characterized by a moist boundary layer. The diurnal error in AIRS PWV at the SGP site seen with respect to the MWR data are confirmed by PWV amounts derived from a coincident ground-based GPS receiver.