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Vegetation water content (VWC) is an important biophysical parameter and has a significant role in the retrieval of soil moisture using microwave remote sensing. Here, the radar vegetation index (RVI) was evaluated for estimating VWC. Analysis utilized a data set obtained by a ground-based multifrequency polarimetric scatterometer system, with a single incidence angle of 40°, during an entire growth period of rice and soybean. Temporal variations of the backscattering coefficients for the L-, C-, and X-bands, RVI, VWC, leaf area index, and normalized difference vegetation index were analyzed. The L-band RVI was found to be correlated to the different vegetation indices. Prediction equations for the estimation of VWC from the RVI were developed. The results indicated that it was possible to estimate VWC with an accuracy of 0.21 kg·m-2 using L-band RVI observations. These results demonstrate that valuable new information can be extracted from current and future radar satellite systems on the vegetation condition of two globally important crop types. The results are directly applicable to systems such as the proposed NASA Soil Moisture Active Passive satellite.