Despite chronic contamination, long-term organic fertilization tends to decrease copper (Cu) and zinc (Zn) availability in agricultural soils. Root activities of crop plants can also induce substantial changes in rhizosphere chemistry and consequently in the Cu and Zn availability in the rhizosphere. The balance between these two drivers and the overall effect of organic fertilization on Cu and Zn bioavailability to plants (i.e., phytoavailability) remains a matter of debate. We assessed the effect of a decade of agronomically realistic organic fertilization on Cu and Zn availability in the rhizosphere and their phytoavailability. Using a laboratory biotest, Festuca arundinacea was exposed to 34 soil samples collected from three agricultural field trials that had received no, mineral, or organic fertilization for a decade. Dissolved organic matter (DOM) properties (i.e., concentration, aromaticity, and binding properties toward Cu), pH, and Cu and Zn availability (i.e., total dissolved concentration and free ionic activity) were determined in the rhizosphere solutions. Cu and Zn phytoavailability was measured as the plant uptake flux. Contrary to bulk soils, organic fertilization induced very few changes in the chemistry and Cu and Zn availability in the rhizosphere solutions compared to no and mineral fertilization. Consistently, Cu and Zn phytoavailability did not increase with organic fertilization, but it was mostly driven by soil properties rather than by fertilization. Despite increasing soil Cu and Zn contamination, a decade of soil organic fertilization did not increase Cu and Zn phytoavailability, presumably due to the root-mediated levelling of Cu and Zn availability in the rhizosphere.