The Archean Madawara Igneous Complex (MIC) comprises a suite of ultramafic-mafic rocks, like serpentinized dunites, harzburgites, wehrlites, peridotites, schists, gabbros, and pegmatitic gabbros. Petrographic and mineralogical investigations reveal vanadium-bearing chromite (1700–7520 ppm), ilmenite (~40000 ppm), magnetite (400–4110 ppm), and titanite (35540–37810 ppm) assemblages from spatially and temporally distinct rock suites within the MIC of the Bundelkhand Granitoid Complex. These oxides exhibit vanadium enrichment, while ilmenite is further distinguished by elevated manganese content. Further, this study suggests that these rocks have experienced postmagmatic alteration processes such as low-temperature hydrothermal alterations and greenschist to amphibolite-facies metamorphism, resulting in extensive replacement of primary minerals, particularly in ultramafic rocks. Mineralogical associations suggest that both magmatic and post-magmatic processes contributed to and affected the formation of Fe-Ti-V-type oxide assemblages. In mafic rocks, element partitioning and sequestration were mainly governed by magmatic differentiation, exsolution, and fractionation, with insignificant crustal contamination. In contrast, ultramafic rocks have signatures of more pronounced post-crystallization modifications. Vanadium enrichment in the oxide phases reflects variable fO₂ and fH₂O conditions and hence suggests redox control redistribution during the metamorphic and hydrothermal alteration of primary silicates and chromite phases. It is also supported by variations in redox-sensitive ratios such as V/Ti and V/Sc. The spatial and compositional segregation of vanadium and manganese-bearing phases across the rock units indicates derivation from a depleted mantle source that was probably affected by metasomatized lithospheric mantle during subduction.