Forest biomass plays an essential role in forest carbon reservoir studies, biodiversity protection, forest management, and climate change mitigation actions. Synthetic Aperture Radar (SAR), especially the polarimetric SAR with the capability of identifying different aspects of forest structure, shows great potential in the accurate estimation of total and component forest above-ground biomass (AGB), including stem, bark, branch, and leaf biomass. This study aims to fully explore the potential of polarimetric parameters at the C- and L-bands to achieve high estimation accuracy and improve the estimation of AGB saturation levels. In this study, the backscattering coefficients at different polarimetric channels and polarimetric parameters extracted from Freeman2, Yamaguchi3, H-A-Alpha, and Target Scattering Vector Model (TSVM) decomposition methods were optimized by a random forest algorithm, first, and then inputted into linear regression models to estimate the total forest AGB and biomass components of two test sites in China. The results showed that polarimetric observations had great potential in total and component AGB estimation in the two test sites; the best performances were for leaves at test site I, with R2 = 0.637 and RMSE = 1.27 t/hm2. The estimation of biomass components at both test sites showed obvious saturation phenomenon estimation according to their scatter plots. The results obtained at both test sites demonstrated the potential of polarimetric parameters in total and component biomass estimation.