Precambrian mafic magmatism is an important global episode which played a significant role in the crustal evolution. In India, Singhbhum Craton being the oldest craton, witnessed significant occurrences of Precambrian geological activity, marked by several episodes of volcanism, plutonism, sedimentation spanning from Palaeoarchean to Mesoproterozoic age. Here we present petrological and geochemical characteristics of Precambrian mafic volcanic rocks (occurring in western Iron Ore Group (IOG), Singhbhum Craton, eastern India) to evaluate their petrogenetic aspects, tectonic setting, and magma generation. The mafic volcanic rocks are porphyritic in nature with the phenocrysts of plagioclase and groundmass composed of clinopyroxene, plagioclase, ilmenite, and volcanic glass. These rocks are mostly tholeiitic, sometimes with a transitional behaviour towards calc‐alkaline nature and display basalt‐basaltic andesite affinity. These mafic volcanic rocks also preserve geochemical signatures (high Nb/U, Nb/La, [Nb/Th]pm ratios) in support of Nb‐enriched basalts and are classified as Nb‐enriched basalts (NEB; Nb > 7 ppm) and high‐Nb basalts (HNB; Nb > 20 ppm) on the basis of Nb concentrations and mantle normalized Nb/La ratios (>0.5). The NEBs and HNBs are marked by lesser magnitude of negative Nb anomalies with high (Nb/Th)pm, (Nb/La)pm, and Nb/U ratios as compared to normal arc basalts. Several major element oxides, trace elements, and selected element ratios (like SiO2, CaO/Al2O3, Y, V/Cr, Zr/Nb, and ∑REE) show systematic variations with MgO which suggests role of magmatic fractionation. Chondrite‐normalized REE patterns for NEB and HNB rocks exhibit uniform LREE enrichment with distinct Eu negative anomalies while primitive mantle‐normalized incompatible trace element patterns reflect enrichment in LILE and LREE with prominent Nb‐Ta anomalies. Different HFSE ratios corroborate a subduction related setting for magma generation formed by ∼10%–20% melting in the domain of garnet lherzolite. Relative enrichment of LILE and LREE with depleted HFSE characteristics attest a garnet‐bearing mantle source and melt extraction with garnet in the residue. Geochemical signatures suggest that the genesis of NEB and HNB is attributable to slab‐melting and wedge hybridization processes during matured stages of subduction. Selected incompatible trace element ratios for the studied mafic volcanic rocks invoke an enriched (EM1‐EM2 type) mantle source and unequivocally suggest effects of continental crustal assimilation of the parent magma. Liquid immiscibility has played an important role as a differentiation mechanism leading to presence of high and low FeO types. The IOG mafic volcanic rocks preserve distinct geochemical signatures of matured stage of subduction, slab melting, crustal contamination and magma generation at an Archean ocean–continent convergent margin setting.