The capability of COSMO-SkyMed in estimating vegetation biomass has been investigated in this paper. SAR data from COSMO-SkyMed were collected on two agricultural areas in Italy in 2010 at different dates during the vegetation cycle. The performances of X-band data have been compared with accurate ground truth measurements of soil and vegetation carried out simultaneously to satellite passes. Experimental data have been compared with model simulations obtained with a discrete element radiative transfer model. Moreover, an inversion algorithm, based on an Artificial Neural Network and trained by using AIEM and the radiative transfer model, has been applied to retrieve the plant water content of wheat and sunflower crops and to generate the corresponding plant water content maps.