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Passive sampling is a rapidly developing technology, which is widely used for the monitoring of pollutants in different environments. Passive sampling offers significant advantages over traditional grab sampling. In the present review, the authors summarize the current literature on the methods of passive sampling used in the environmental monitoring of polar or semi-polar compounds in aqueous matrices. Methods of calibrating, design and deployment of samplers are also discussed. A major focus of this review is the use of polar organic compound integrative samplers (POCIS) and their use in sampling and monitoring of pharmaceuticals and personal care products (PCPs) in both equilibrium and non-equilibrium conditions.