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Passive sampling is one of the most efficient methods of monitoring pharmaceuticals in environmental water. The reliability of the process relies on a correctly performed calibration experiment and a well-defined sampling rate (Rs) for target analytes. Therefore, in this review the state-of-the-art methods of passive sampler calibration for the most popular pharmaceuticals: antibiotics, hormones, β-blockers and nonsteroidal anti-inflammatory drugs (NSAIDs), along with the sampling rate variation, were presented. The advantages and difficulties in laboratory and field calibration were pointed out, according to the needs of control of the exact conditions. Sampling rate calculating equations and all the factors affecting the Rs value - temperature, flow, pH, salinity of the donor phase and biofouling were discussed. Moreover, various calibration parameters gathered from the literature published in the last 16 years, including the device types, were tabled and compared. What is evident is that the sampling rate values for pharmaceuticals are impacted by several factors, whose influence is still unclear and unpredictable, while there is a big gap in experimental data. It appears that the calibration procedure needs to be improved, e.g. there is a significant deficiency of PRCs (Performance Reference Compounds) for pharmaceuticals. One of the suggestions is to introduce correction factors for Rs values estimated in laboratory conditions.