We present a generic theoretical model (MICROWEB) that simulates the transfer of microplastics and hydrophobic organic chemicals (HOC) in food webs. We implemented the model for an Arctic case comprised of nine species including Atlantic cod, with polar bear as top predator. We used the model to examine the effect of plastic ingestion on trophic transfer of microplastics and persistent HOCs (PCBs) and metabolizable HOCs (PAHs), spanning a wide range of hydrophobicities. In a scenario where HOCs in plastic and water are at equilibrium, PCBs biomagnify less when more microplastic is ingested, because PCBs biomagnify less well from ingested plastic than from regular food. In contrast, PAH biomagnify more when more microplastic is ingested, because plastic reduces the fraction of PAH available for metabolisation. We also explore non-equilibrium scenarios representative of additives that are leaching out, as well as sorbing HOCs, quantitatively showing how the above trends are strengthened and weakened, respectively. The observed patterns were not very sensitive to modifications in the structure of the food web. The model can be used as a tool to assess prospective risks of exposure to microplastics and complex HOC mixtures for any food web, including those with relevance for human health.