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The release of petroleum liquids in water, such as marine, riverine, and lacustrine basins, is a matter of concern that shoves authorities and experts to adopt technical approaches for preventing damages, monitoring oil content in water and cleaning up environmental aqueous matrices. In this paper, a dedicated system for oil spill detection is presented. The proposed system consists of an optical fiber sensor and an image processing unit useful to steer and optimize the measurement process. An optical fiber-based antenna sensor is used to detect the oil concentration in water. The sensor consists of two slanted optical probes acting as transmitter and receiver, respectively. Both probes are completely immersed into water being analyzed. The sensing approach is based on the measurement of the light coupling level affected by the reflectivity of the oil layer floating on the water surface. The experimental measurement of different types of oil is performed to assess the sensitivity of the developed system. Special attention is put on the image postelaboration useful to derive the characteristics of the oil distribution on the water surface. In this respect, two different image processing techniques are considered: the first one is based on a suitable energy-minimizing spline fitting procedure subject to external constraint forces, whereas a judicious use of the Hough transform is made in the second one.