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Here, four normalized difference water index (NDWI) variants, i.e., NDWI(860,970), NDWI(860,1240), NDWI(860,1640), and NDWI(1240,1640) are generated from the corn-oriented PROSAIL radiative transfer model. It is found that, instead of the linear relationship derived in previous studies, corn canopy water content (CWC) is best approximated as an exponential function of NDWI. Following the analysis of the PROSAIL-generated results, a newly optimized NDWI-based scheme is proposed for estimating corn CWC according to variations in the performance of the four NDWI variants under different CWC conditions. Validation results based on independent field data from the SMEX02, HiWATER2012, and Baoding2018 field experiments verify that this optimized NDWI-based corn CWC estimating scheme has a higher accuracy ($R = 0.87\,\,\pm \,\,0.03$ , RMSE = 0.2068 ± 0.0145 kg/m2) than existing NDWI-based strategies for corn CWC retrieval. The feasibility of retrieving corn vegetation water content (VWC) based on the optimized NDWI-based scheme is also investigated, and the superiority of the optimized NDWI-based scheme for retrieving corn VWC is assessed. By comparing with four other NDWI-based corn VWC estimating methods, as well as the corn VWC parameterization scheme applied in the SMAP soil moisture algorithm, it is shown that our optimized NDWI-based scheme has the best VWC estimation accuracy, with the highest $R$ of 0.89 ± 0.02 and the lowest RMSE of 0.7179 ± 0.0555 kg/m2. [ABSTRACT FROM AUTHOR]