Competitive interactions between silicate and phosphate at ligand exchange sites in the sediment surface layer may increase the release of phosphorus (P) from the sediment into the water column. In this study, the role of silicon (Si) in the release of P from the sediment surface layer was studied in a marine estuarine environment, the Bay of Brest, with the aid of a sequential sediment fractionation procedure developed for P, and the addition of inorganic or diatom-bound Si to surface sediment samples in vitro. The potentially mobile pools of P in the surface sediment (loosely bound P + Fe/Al-bound-P) amounted to 5.0 μmol g−1 dry sed., 42% of the total extractable and 33% of the total amount of P in the sediment, while the similarly extracted pools of Si were bigger (ca. 20 μmol g−1 dry sed., 50% of the total extractable Si). Additions of inorganic Si increased the concentration of dissolved P in the sediment interstitial water in a bottle experiment, and the addition of both inorganic Si and cultivated diatoms to intact sediment cores increased the outward flux of dissolved P. Model calculations based on the regression equation from the bottle experiment and Si and P water column data showed that the sedimentation of spring diatoms could cause Si pulses to the sediment which would produce a P flux to the water column of ca. 44 μmol m−2 d−1. Field data from the bay show that in spring, decreases in P and Si and an increase in chl a due to diatom production are often followed by a small separate P peak which may be caused by Si-induced P fluxes from the sediment surface.