This paper presents a method to characterize snow cover in mountainous regions using dual-polarization C-band synthetic aperture radar (SAR) data. It is demonstrated that an accurate modeling of the liquid water distribution inside the snowpack, using a multilayer meteorological snow model, is required to characterize snow with precision. A multilayer-snow electromagnetic (EM) backscattering model is developed based on the vector radiative transfer, the strong fluctuation theory, and physical parameters supplied by the meteorological model. However, the limited resolution of the meteorological snow model is insufficient for predicting a refined EM backscattering at a massif scale. An adequate spatial reorganization of these snow profiles, based on a comparison between simulated and measured dual-polarization SAR data, leads to a better estimation of some snowpack parameters. In particular, the monitoring of snow liquid water content is presented improving the capacity of wet snow mapping as compared to a classical SAR-based method. This methodology shows good capacities both for qualitative and quantitative snow assessments, opening the way for a new operational method.