This paper takes thin oil film on the sea surface in oil spill pollution as the subject of our research. Combined with physical characteristics of the target, the Mueller matrix of the target is analyzed via a polarization technique. The paper uses the Mueller matrix derived from the Mueller-Jones matrix. Based on the Mueller-Jones matrix, the optical recognition model of oil film on the sea surface is established. This paper proposes a multiangle polarization measurement technology for oil spill pollution on the sea surface and proposes a new data processing method. By calculating the corresponding amplitude ratio, phase retardation, refractive index, and degree of polarization of each pixel, the optical properties of the oil film on the sea surface are analyzed; the surface characteristics of oil film on the sea surface are extracted; the calculation accuracy is improved; and ocean oil spill optical recognition is developed.