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Rice is a major food supply in southeast China. With increased population and urbanization, reliable rice mapping is critical in this region. Because of frequent cloud cover and precipitation during the rice-growing season, it is difficult to conduct large-area rice monitoring with optical remote sensing techniques. L-band synthetic aperture radar (SAR), with its all-weather day and night imaging and canopy penetration capabilities, provides a unique alternative. In this study, a first-order radiative transfer model was developed to simulate L-band scattering properties of paddy rice. Three Advanced Land Observing Satellite (ALOS)/Phased-Array-Type L-band Synthetic Aperture Radar (PALSAR) images in dual-polarization mode (HH and HV) acquired in early tillering (June 28, 2007), tillering (August 13, 2007), and heading (September 28, 2007) stages were processed to test the temporal variation of rice backscatter. It was found that plant height and leaf mass amount were the two major structural parameters that contributed to rice backscatter in PALSAR images. The variation of the simulated HH backscatter matched with PALSAR observations in sample fields, although the simulated backscatter coefficients were around 3 dB lower than image-extracted values. Leaf volume scattering and leaf-ground double bounce were found as the two major scattering components in L-band HH polarization and increased with leaf layer height and density. This paper demonstrated that L-band HH backscatter was more sensitive to rice's structural variation than the VV backscatter and may therefore be more useful in rice mapping and modeling studies.