Remote sensing is an important method for monitoring marine oil-spill accidents. However, methods for measuring oil-film thickness remain insufficient. Due to the stable differences in the surface emissivity and temperature of oil and water, the oil film can be detected using thermal infrared. This study measured emissivity of seven different oil-film thicknesses and seven different American Petroleum Institute (API) densities, and analyzed the spectral characteristics. Results show an optimal wavelength position for oil-film thickness and fuel API density monitoring is 12.55 μm. Principal component analysis and continuum removal methods were used for data processing. Stepwise multiple linear regression was used to establish relationships between emissivity and oil slick thicknesses and API densities. Oil-film thickness and fuel API density data were analyzed by principal component analysis and continuum removal before regression analysis. The spectral emissivity data was convolved into Advanced Spaceborne Thermal Emission and Reflection Radiometer (ASTER) and Advanced Very High Resolution Radiometer (AVHRR) thermal bands to determine potential of the sensor in oil-film detection. The result shows that neither could be used to estimate thickness. The AVHRR-4 band and band 12 and 13 of the ASTER could be used to separate oils from water and have potential to distinguish different oil types.