This study aimed at relating the variability of Ni biogeochemistry along the ultramafic toposequence to pedogenesis and soil mineralogy. Hypereutric Cambisols dominate upslope; Cambic Vertisols and Fluvic Cambisols occur downslope. The soil mineralogy showed abundance of primary serpentine all over the sequence. It is predominant upslope but secondary smectites dominate in the Vertisols. Free Fe-oxides are abundant in all soils but slightly more abundant in the upslope soils. Whereas serpentines hold Ni in a similar and restricted range in every soil (approx. 0.3 %), Ni contents in smectites may vary a lot and Mg-rich and Al-poor smectites in the Vertisol could hold up to 4.9 % Ni. Ni was probably adsorbed onto amorphous Fe-oxides and was also exchangeable in secondary smectites. High availability of Ni in soils was confirmed by DTPA extractions. However, it varied significantly along the toposequence, being higher in upslope soils, where Ni-bearing amorphous Fe-oxides were abundant and total organic carbon higher and sensibly lower downslope on the Vertisols: NiDTPA varied from 285 mg kg(-1) in the surface of soil I (upslope) to 95.9 mg kg(-1) in the surface of Fluvic Cambisols. Concentration of Ni in Alyssum murale shoots varied from 0.7 % (Hypereutric Cambisols) to 1.4 % (Hypereutric Vertisol). Amazingly, Ni uptake by A. murale was not correlated to NiDTPA, suggesting the existence of specific edaphic conditions that affect the ecophysiology of A. murale upslope.