The storage capacity, trophic magnification and risk of sixty-two POPs have been evaluated in a well-characterized pelagic food web (including phytoplankton, zooplankton, six fish, and two cephalopods species) from an impacted area in NW Mediterranean Sea. Our results show the high capacity of the planktonic compartment for the storage of polybrominated diphenyl ethers (PBDEs) and polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), consistent with their estimated low trophic magnification factors (TMF) of 0.2–2.0 (PBDEs) and of 0.3–1.1 (PCDD/Fs). ∑PBDEs dominated in the zooplankton size-class 200–1000 μm (∼330 ng g–1 lw, median), whereas ∑PCDD/Fs accumulated preferentially in phytoplankton size-class 0.7–200 μm (875 pg g–1 lw, median). In contrast, polychlorinated biphenyls (PCBs) were preferentially bioaccumulated in the higher trophic levels (six fish species and two cephalopods) with TMFs = 0.8–3.9, reaching median concentrations of 4270 and 3140 ng g–1 lw (∑PCBs) in Atlantic bonito (Sarda sarda) and chub mackerel (Scomber colias), respectively. For these edible species, the estimated weekly intakes of dioxin-like POPs for humans based on national consumption standards overpassed the EU tolerable weekly intake. Moreover, the concentrations of nondioxin-like PCBs in S. sarda were above the EU maximum levels in foodstuffs, pointing to a risk. No risk evidence was found due to consumption of all other edible species studied, neither for PBDEs. The integrated burden of POPs in the food web reached ∼18 μg g–1 lw, representing a dynamic stock of toxic organic chemicals in the study area. We show that the characterized food web could be a useful and comprehensive “bioindicator” of the chemical pollution status of the study area, opening new perspectives for the monitoring of toxic chemicals in Mediterranean coastal waters.