Reliable measurements of soil moisture at global scale might greatly improve many practical issues in hydrology, meteorology, climatology or agriculture such as water management, quantitative precipitation forecasting, irrigation scheduling, etc. Remote sensing offers the unique capability to monitor soil moisture over large areas but, nowadays, the spatio-temporal resolution and accuracy required for some hydrological applications (e.g., flood forecasting in medium to large basins) have still to be met. The Advanced SCATterometer (ASCAT) onboard the Metop satellite (VV polarization, C-band at 5.255 GHz), based on a large extent on the heritage of the ERS scatterometer, provides a soil moisture product available at a coarse spatial resolution (25 km and 50 km) and at a nearly daily time step. This study evaluates the accuracy of the new 25 km ASCAT derived saturation degree product by using in situ observations and the outcomes of a soil water balance model for three sites located in an inland region of central Italy. The comparison is carried out for a 2-year period (2007–2008) and three products derived from ASCAT: the surface saturation degree, ms, the exponentially filtered soil wetness index, SWI, and its linear transformation, SWI*, matching the range of variability of ground data. Overall, the performance of the three products is found to be quite good with correlation coefficients higher than 0.92 and 0.80 when the SWI is compared with in situ and simulated saturation degree, respectively. Considering SWI*, the root mean square error is less than 0.035 m3/m3 and 0.042 m3/m3 for in situ and simulated saturation degree, respectively. More notably, when the ms product is compared with modeled data at 3 cm depth, this index is found able to accurately reproduce the temporal pattern of the simulated saturation degree in terms of both timing and entity of its variations also at fine temporal scale. The daily temporal resolution and the reliability obtained with the ASCAT derived saturation degree products represent the preliminary step for its effective use in operational rainfall-runoff modeling.