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The use of the visible and near infrared (VNIR) bands of MODIS and MERIS imaging sensors acquired in sunglint conditions to reveal smoothed regions such as those affected by oil pollution is investigated. The underlying physical mechanism that enables oil slick detection is based on the modification of the surface slope distribution composing the wind-roughened sea due to the action of mineral oils. The role of sunglint as the chief mechanism that allows the imaging of oil slick features with VNIR wavelengths is assessed for selected case studies in the Mediterranean Sea. The high rate of acquisition and the frequent occurrence of MODIS and MERIS imagery affected by sunglint, especially in low-latitude seas, can thus significantly contribute to increase the actual oil slick detection capability offered by synthetic aperture radar (SAR) systems. We also show how the combined observations from any of the microwave and optical sensors permit the slick to be followed during its movement. Finally, a simulation study specific to the Mediterranean Sea was carried out in order to demonstrate the feasibility of such an approach supporting SAR observations.