The Polar Organic Chemical Integrative Samplers (POCIS) is the most widely used passive sampler for hydrophilic compounds, but unsuitable for certain ionic organic contaminants. The Diffusive Gradient in Thin-Film technique (o-DGT) has shown positive results for both ionic and hydrophilic compounds. However, a calibration step is now needed to evaluate kinetic constant of accumulation for a wide range of molecules. In this study, o-DGT and POCIS were compared for the sampling of three families of micropollutants of potential risk to aquatic environments: 53 pesticides, 36 pharmaceuticals and 20 hormones. A calibration experiment was conducted to compare the kinetic models and constants from a scientific and practical perspective. The results are discussed in a single table that summarizes the performance of both passive samplers for the 109 compounds of interest. The advantage of o-DGT is that it allows linear accumulation for 72 compounds versus only 33 with POCIS. The mean times to equilibrium obtained with o-DGT are higher than those obtained with POCIS. These results confirm that the presence of a diffusion gel delays the achievement of equilibrium during compound accumulation. Therefore, o-DGT can be considered for situations where POCIS cannot be used due to non-linear accumulation over a typical 14-day deployment period. However, overall sampling rates and mass transfer coefficients also appear reduced with o-DGT, which is explained by the smaller exchange surface area, as well as the consideration of an additional diffusive layer in this device. This paper also showed that the most appropriate membrane to sample polar compounds with o-DGT was a polyethersulfone polymer with a pore size of 5 μm.