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The Naval Research Laboratory WindSat polarimetric radiometer was launched on January 6, 2003 and is the first fully polarimetric radiometer to be flown in space. WindSat has three fully polarimetric channels at 10.7, 18.7, and 37.0 GHz and vertically and horizontally polarized channels at 6.8 and 23.8 GHz. A first-generation wind vector retrieval algorithm for the WindSat polarimetric radiometer is developed in this study. An atmospheric clearing algorithm is used to estimate the surface emissivity from the measured WindSat brightness temperature at each channel. A specular correction factor is introduced in the radiative transfer equation to account for excess reflected atmospheric brightness, compared to the specular assumption, as a function wind speed. An empirical geophysical model function relating the surface emissivity to the wind vector is derived using coincident QuikSCAT scatterometer wind vector measurements. The confidence in the derived harmonics for the polarimetric channels is high and should be considered suitable to validate analytical surface scattering models for polarized ocean surface emission. The performance of the retrieval algorithm is assessed with comparisons to Global Data Assimilation System (GDAS) wind vector outputs. The root mean square (RMS) uncertainty of the closest wind direction ambiguity is less than 20° for wind speeds greater than 6 m/s and less than 15° at 10 m/s and greater. The retrieval skill, the percentage of retrievals in which the first-rank solution is the closest to the GDAS reference, is 75% at 7 m/s and 85% or higher above 10 m/s. The wind speed is retrieved with an RMS uncertainty of 1.5 m/s.