Oil spill detection has attracted increasing attention in recent years since marine oil spill accidents severely affect environments, natural resources, and the lives of coastal inhabitants. Hyperspectral remote sensing images provide rich spectral information which is beneficial for the monitoring of oil spills in complex ocean scenarios. However, most of the existing approaches are based on supervised and semi-supervised frameworks to detect oil spills from hyperspectral images (HSIs), which require a huge amount of effort to annotate a certain number of high-quality training sets. In this study, we make the first attempt to develop an unsupervised oil spill detection method based on isolation forest for HSIs. First, considering that the noise level varies among different bands, a noise variance estimation method is exploited to evaluate the noise level of different bands, and the bands corrupted by severe noise are removed. Second, kernel principal component analysis (KPCA) is employed to reduce the high dimensionality of the HSIs. Then, the probability of each pixel belonging to one of the classes of seawater and oil spills is estimated with the isolation forest, and a set of pseudo-labeled training samples is automatically produced using the clustering algorithm on the detected probability. Finally, an initial detection map can be obtained by performing the support vector machine (SVM) on the dimension-reduced data, and then, the initial detection result is further optimized with the extended random walker (ERW) model so as to improve the detection accuracy of oil spills. Experiments on airborne hyperspectral oil spill data (HOSD) created by ourselves demonstrate that the proposed method obtains superior detection performance with respect to other state-of-the-art detection approaches.