Synthetic aperture radar (SAR) is an important means to detect ocean oil spills which cause serious damage to the marine ecosystem. However, the look-alikes, which have a similar behavior to oil slicks in SAR images, will reduce the oil spill detection accuracy. Therefore, a novel oil spill detection method based on multiple features of polarimetric SAR data is proposed to improve the detection accuracy in this paper. In this method, the self-similarity parameter, which is sensitive to the randomness of the scattering target, is introduced to enhance the discrimination ability between oil slicks and look-alikes. The proposed method uses the Random Forest classification combing self-similarity parameter with seven well-known features to improve oil spill detection accuracy. Evaluations and comparisons were conducted with Radarsat-2 and UAVSAR polarimetric SAR datasets, which shows that: (1) the oil spill detection accuracy of the proposed method reaches 92.99% and 82.25% in two datasets, respectively, which is higher than three well-known methods. (2) Compared with other seven polarimetric features, self-similarity parameter has the better oil spill detection capability in the scene with lower wind speed close to 2–3 m/s, while, when the wind speed is close to 9–12 m/s, it is more suitable for oil spill detection in the downwind scene where the microwave incident direction is similar to the sea surface wind direction and performs well in the scene with incidence angle range from 29.7° to 43.5°.