Six field trials were carried out to assess the performance of the Chemcatcher passive sampler alongside spot sampling for monitoring priority hydrophobic organic pollutants (polycyclic aromatic hydrocarbons (PAHs) and organochlorine pesticides) in a wide range of conditions in surface water. The trials were performed in three European rivers: Elbe (Czech Republic), Alna (Norway) and Meuse (Netherlands), in two seasons (April–June 2004, and September–October 2004). Samplers spiked with performance reference compounds (PRCs) were deployed for either 14 or 28 days. Ten spot samples of water were collected over the course of the trial and filtered through a 0.7 μm glass fibre filter. Concentrations of pollutants measured using the Chemcatcher were compared with the average concentrations found in spot samples. This study describes the operational performance of Chemcatcher for measuring hydrophobic (log KOW 3.7–6.8) chemicals in surface water. Site specific Chemcatcher sampling rates up to 0.5 L d−1 were found using the PRC approach that reduced the uncertainty in estimates of sampling kinetics where temperature, local flow conditions and biofouling potential varied between sites and seasons, and with time during sampler exposure. The limits of quantification of sampled analytes ranged from one to tens ng L−1. Highest sensitivity was achieved for compounds with a favourable combination of low instrument quantification limits and high sampling rates including dieldrin, hexachlorobenzene, lindane, pentachlorobenzene, and PAHs with less than five aromatic rings. The direct comparison of time weighted average (TWA) concentrations (mostly close to method limits of detection) obtained using passive and spot sampling was possible for lindane, hexachlorobenzene, and PAHs < 4 rings. Implications of using the Chemcatcher in regulatory monitoring programmes such as the European Union Water Framework Directive are discussed.