Abstract: The western Henan hosted large-scale diasporic karst bauxite deposits in the Late Carboniferous formations, characterized by abundant rare, dispersed, and rare earth elements, along with high abundances of lithium and niobium-tantalum. Focusing on six bauxite deposits in western Henan, this paper, based on their robust geological data, examines the correlations of lithium and niobium-tantalum with the primary chemical components of ores. Meanwhile, using X-ray diffraction (XRD) and scanning electron microscopy (SEM) methods, it investigated the distribution and enrichment mechanisms of lithium and niobium-tantalum in aluminum-bearing rock series. The results show that lithium and niobium-tantalum exhibited positive correlations with the primary chemical components in bauxites and roof clay rocks, with significantly different correlations observed in the floor ferrous clay rocks. This implies the complexity of provenances of the aluminum-bearing rock formations. In addition, in the roof clay rocks, bauxites, and floor ferrous clay rocks, the content of lithium was positively correlated with that of niobium-tantalum. This demonstrates that they share substantially identical enrichment mechanisms during deposition and the same or overlapping ore-forming provenances. This study demonstrates the possibility of associated lithium and niobium-tantalum in the study area evolving into industrial deposits, filling the gap in research on their enrichment mechanisms in the aluminum-bearing rock series, western Henan. The study area holds significant potential for lithium and niobium-tantalum resources, which will bring enormous economic benefits. Therefore, further mineral exploration should be carried out here.