Marine oil spill pollution has caused serious impacts on marine ecological environments, ecological resources and marine economy. Synthetic Aperture Radar (SAR), especially polarmetric SAR (PolSAR), has been proven to be a powerful and efficient tool for marine oil spill detection. In general, traditional oil spill detection methods mainly rely on artificially-extracted polarization characteristics, and the detection accuracy is limited by the quality of feature extraction. Recently proposed Convolutional neural network (CNN) is capable of mining spatial feature from large data set automatically. Inspired by these, in this paper we proposed a novel oil spill identification method based on multi-layer deep feature extraction by CNN. Firstly, PolSAR data are converted into a 9-channel data block to feed the CNN. Then, a 5-layer CNN architecture is built to extract two high-level features from the original data automatically. The features are fused after dimension reduction via principal component analysis (PCA). Finally, support vector machine method with radial basis function kernel (RBF-SVM) is utilized for classification. Three sets of RADARSAT-2 fully polarimetric SAR data were used in this study to validate the proposed method. The obtained results reveal that the proposed method provides competitive results in overall classification accuracy and kappa coefficient. Moreover, this method can improve the accuracy of oil spill detection, reduce the false alarm rate, and effectively distinguish an oil spill from a biogenic slick. INDEX TERMS Marine oil spill, RADARSAT-2, PolSAR, deep learning, feature extraction, convolutional neural network (CNN).