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This paper addresses the capability of synthetic aperture radar and optical images in combination with theoretical models to detect the vegetation water content (VWC) at field level. In this paper, a retrieval algorithm for the estimation of VWC from AirSAR acquired on vegetated fields during the SMEX'02 experiment is addressed. The aforementioned campaign has been chosen because, along with sensor observations, extensive ground truth measurements were acquired. The retrieval procedure, which is based on a Bayesian approach, has been initially developed for soil moisture extraction. It consists of two modules: one is pertinent to bare soils and the other one has been modified for vegetated fields. The last one uses the synergy with optical images to correct for the contribution of VWC. The VWC, a variable in the inversion procedure, as well as soil moisture can be estimated. The results indicate a good correlation with both ground measurements and VWC calculated from Landsat images through the use of normalized difference water index (NDWI). Furthermore, in the inversion procedure, the introduction of the dependence on roughness improves the estimates. This indicates that, even for dense vegetation, the contribution from bare soil greatly influences the radar signal. Three main levels of VWC are discriminated in the inversion procedure: values below 1 kg/m2, values between 1 and 3 kg/m2, and values greater than 3 kg/m2.