The influence of microbial activity on the concentration and speciation of trace elements (TEs) was assessed in a study on the bioavailability of TEs for edible plants. A growth chamber experiment with spring wheat (Triticum aestivum cv. USU-Perigee) was conducted and the bulk (Bk) and the rhizosphere (Rz) soil components were collected at maturity. A characterization of the microbial activity and population was made by measuring the microbial biomass, enzymes (acid phosphatase, arylsulfatase, dehydrogenase and urease) and 16S rDNA DGGE profiles. In soil water extracts, major solutes (H+, Ca, Mg, Na, NH4, K, Cl, NO3, SO4, total N, DON and DOC) and trace elements (Al, As, Cd, Ce, Cr, Cu, Fe, Pb, Tl, and Zn) including monomeric Al species, free Cu2+ and labile Zn were determined. The partition of the variation indicated that 12.1% of the distribution of TEs in the Bk soil was significantly and exclusively explained by chemical properties while this value was less than 0.1% for the Rz soil. To the contrary, microbial properties contributed significantly to 12.3% of the distribution of TEs in the Rz soil whereas it explained less than 0.1% for the Bk soil. Detailed redundancy analyses identified several potential mechanisms (e.g. weathering of primary mineral, solubilisation of sesquioxides, bacterial effect on the redox status) explaining the fate of TEs in the Bk and Rz soils. This study revealed that microbial activity is strongly associated to the speciation of trace elements in the Rz of edible plants and points to some microbial processes influencing TE speciation.