In the southern Aosta Valley (Italian Western Alps), several massive magnetite bodies occur within serpentinized ultramafic rocks belonging to the Mesozoic meta-ophiolite nappe. The ultramafic rocks consist of lherzolite with minor dunite bodies and show a high pressure metamorphic overprint. The results of a multi-methodological study, based on optical microscopy, electron microprobe analysis and single-crystal X-ray diffraction, are reported here in order to give new insights into (1) the mineralogy and crystal chemistry of spinels and silicates and (2) the genesis of the massive magnetite bodies. Chromium-rich relict cores inside the magnetite grains suggest a derivation from primary chromite concentrations. The major-element behaviour shows the presence of two chromite types: a Cr2O3-rich (Al2O3-poor) type and a Cr2O3-poor (Al2O3-rich) type. Magnetite ore deposits probably represent the product of transformation from a chromite proto-ore which formed in ultramafic rocks pertaining to an ophiolite suite. The transformation of chromite to magnetite occurred during multiple stages: the premetamorphic setting of the ultramafics and the petrographic evidence suggest that metasomatism started before the onset of the alpine metamorphism and was active during the early alpine, eclogitefacies metamorphic overprint related to a subduction process under high fluid activity.