The impact of the ocean surface roughness on the ocean L-band emissivity is investigated using simultaneous airborne measurements from an L-band radiometer (CAROLS) and from a C-band scatterometer (STORM) acquired in the Gulf of Biscay (off-the French Atlantic coasts) in November 2010. Two synergetic approaches are used to investigate the impact of surface roughness on the L-band brightness temperature (Tb). First, wind derived from the scatterometer measurements is used to analyze the roughness contribution to Tb as a function of wind and compare it with the one simulated by SMOS and Aquarius roughness models. Then residuals from this mean relationship are analyzed in terms of mean square slope derived from the STORM instrument. We show improvement of new radiometric roughness models derived from SMOS and Aquarius satellite measurements in comparison with prelaunch models. Influence of wind azimuth on Tb could not be evidenced from our data set. However, we point out the importance of taking into account large roughness scales (>20 cm) in addition to small roughness scale (5 cm) rapidly affected by wind to interpret radiometric measurements far from nadir. This was made possible thanks to simultaneous estimates of large and small roughness scales using STORM at small (7–16°) and large (30°) incidence angles.