We report the first empirical confirmation of the co-occurrence of organophosphate esters (OPEs) additives and microplastics (MPs) in benthic compartments from the Loire estuary. Higher median concentrations of MPs (3387 items/kg dw), ∑13tri-OPEs (12.0 ng/g dw) and ∑4di-OPEs (0.7 ng/g dw) were measured in intertidal sediments with predominance of fine particles, and under higher anthropogenic pressures, with a general lack of seasonality. Contrarily, Scrobicularia plana showed up to 4-fold higher ∑tri-OPE concentrations in summer (reaching 37.0 ng/g dw), and similar spatial distribution. Polyethylene predominated in both compartments. Tris(2-ethylhexyl) phosphate (TEHP), its degradation metabolite (BEHP) and tris-(2-chloro, 1-methylethyl) phosphate (TCIPP) were the most abundant OPEs in sediments, while TCIPP predominated in S. plana. The biota-sediment accumulation factors suggest bioaccumulation potential for chlorinated-OPEs, with higher exposure in summer. No significant correlations were generally found between OPEs and MPs in sediments suggesting a limited role of MPs as in-situ source of OPEs.