We systematically investigated the transport mechanisms of organic micropollutants (OMPs) in a fertilizer-drawn forward osmosis (FDFO) membrane process. Four representative OMPs, i.e., atenolol, atrazine, primidone, and caffeine, were chosen for their different molecular weights and structural characteristics. All the FDFO experiments were conducted with the membrane active layer on the feed solution (FS) side using three different fertilizer draw solutions (DS): potassium chloride (KCl), monoammonium phosphate (MAP), and diammonium phosphate (DAP) due to their different properties (i.e., osmotic pressure, diffusivity, viscosity and solution pH). Using KCl as the DS resulted in both the highest water flux and the highest reverse solute flux (RSF), while MAP and DAP resulted in similar water fluxes with varying RSF. The pH of the FS increased with DAP as the DS due to the reverse diffusion of NH4 + ions from the DS toward the FS, while for MAP and DAP DS, the pH of the FS was not impacted. The OMPs transport behavior (OMPs flux) was evaluated and compared with a simulated OMPs flux obtained via the pore-hindrance transport model to identify the effects of the OMPs structural properties. When MAP was used as DS, the OMPs flux was dominantly influenced by the physicochemical properties (i.e., hydrophobicity and surface charge). Those OMPs with positive charge and more hydrophobic, exhibited higher forward OMP fluxes. With DAP as the DS, the more hydrated FO membrane (caused by increased pH) as well as the enhanced RSF hindered OMPs transport through the FO membrane. With KCl as DS, the structural properties of the OMPs were dominant factors in the OMPs flux, however the higher RSF of the KCl draw solute may likely hamper the OMPs transport through the membrane especially those with higher MW (e.g., atenolol). The pore-hindrance model can be instrumental in understanding the effects of the hydrodynamic properties and the surface properties on the OMPs transport behaviors.