Based on the model of Lombardini et al. [J. Atmos. Ocean. Technol.6(6), 882–890 (1989)], which can predict the hydrodynamic damping of rough sea surfaces in the presence of oil films, the influence of sea slicks on the sea surface roughness spectrum and sea surface geometrical structure is examined briefly in the present study. On this basis, the influence of sea slicks on the angular distribution of the bistatic scattering coefficient of sea surfaces and the Doppler spectrum signature of backscattered radar sea-echo is investigated in detail based on a frequency-domain numerical method of the parallel fast multiple method. Simulation results show that Doppler spectrum signatures including Doppler shift and spectral bandwidth of radar sea-echo are significantly affected by sea slicks, which are qualitatively consistent with wave-tank or open sea measurements. Moreover, simulation results indicate that the Doppler spectrum signature is a promising technique for remote sensing of oil films floating on sea surfaces.