Soil profiles developed on serpentinites from several localities in the Czech Republic were investigated by a combination of geochemical and mineralogical methods (selective extractions, XRD, SEM/EDS) to determine the partitioning and mobility of chromium (Cr) and nickel (Ni). Whereas Cr is released from pyroxenes, amphiboles and Cr-spinels present in the bedrock, Ni is primarily mobilized from olivines and small Fe-Ni sulphide inclusions. The results of extraction methods indicated significant differences in the availability and mobility of Cr and Ni in soils. Chromium is almost not phytoavailable, as indicated by the DTPA extractions. The selective extractions showed that Cr is tightly bound to well-crystallised Fe-oxides and primary rock-derived phases. In contrast, Ni is substantially more mobile in soil, being mainly controlled by Mn-oxides and amorphous/less crystallised Fe-oxides. The DTPA extraction indicated that up to 10% of total Ni might be phytoavailable.