In this study, oil spill experiments were performed in a water tank to determine changes in the surface scattering characteristics during the emulsification of oil spills. A C-band fully-polarimetric microwave scatterometer and a vector network analyzer were used to observe films of the following oils: crude oil with an asphalt content below 3% that is prone to emulsification (type A), fresh crude oil extracted from an oilfield (type B), and industrial crude oil that was dehydrated and purified (type C). The difference in the backscatter results between the emulsified oil film and the calm water surface under C-band microwaves and the influence of the emulsification of the oil film on the backscatter were analyzed in detail. The results demonstrate that under a low-wind and no-waves condition (the maximum wave height was below than 3 mm), the emulsification of crude oil could modulated the backscatter through changes in the surface roughness and the dielectric constant, where the surface roughness had the dominant effect. The surface backscatters of the type B oil were greater than that of the type C oil in both the emulsified and non-emulsified states. In the non-emulsified state, the average differences in the backscatter between the type B and C oils were 2.19 dB, 2.63 dB, and 2.21 dB for the polarization modes of VV, HH, and HV/VH, respectively. Smaller corresponding average differences of 0.98 dB, 1.49 dB, and 1.5 dB were found for the emulsified state with a 20% moisture constant for the oil film. The results demonstrated that the surface roughness of the different oil films could vary due to the differences in the oil compositions and the oil film properties, which in turn affect the backscatter of the oil film surface.