Abstract: As an important supplementary source of strategic mineral resources, critical metals hosted in aluminum-bearing strata have recently attracted considerable attention in the field of mineral exploration. Inspired by the anomalous enrichment of polymetallic elements (e.g., Li and Nb) in clay-type or bauxite-type deposits in southwestern China, increasing interest has focused on the critical metal potential of the iron–aluminum member of the Upper Paleozoic Benxi Formation in the North China Craton. However, as one of the major regions for bauxite resources in North China, the distribution and occurrence of associated critical metals in Yangquan Mining Area remain poorly constrained. The Iron–Aluminum member of the Upper Paleozoic Benxi Formation at Huoshutou, Yangquan, was investigated using an integrated analytical approach combining X-ray powder diffraction (XRD), Siroquant quantitative software, TESCAN Integrated Mineral Analyzer (TIMA), X-ray fluorescence spectroscopy (XRF), and inductively coupled plasma-mass spectrometry (ICP-MS). Petrological, mineralogical, and geochemical characteristics were systematically characterized to elucidate the distribution and occurrence of critical metals. The results indicate that the iron–aluminum member exhibits a co-enrichment of Li, Ga, Zr, Nb, and REY (rare earth elements plus yttrium), with these elements predominantly concentrated in bauxitic rock relative to the overlying clay rock and underlying ferruginous rock. The weighted average concentrations are 1 017 (Li), 58 (Ga), 962 (Zr), 121 (Nb), and 867 μg/g (REY) in the bauxitic rock, respectively. Specifically, Li in both the clay rock and bauxitic rock is mainly hosted in cookeite; Ga is primarily associated with diaspore; Zr and Nb are principally correlated with zircon and anatase; and REY are primarily hosted in phosphate minerals. On a high-temperature ash basis, maximum concentrations of critical metals reach 4 253 μg/g for Li₂O, 92 μg/g for Ga, 1 834 μg/g for (Zr, Hf)O₂, 281 μg/g for (Nb, Ta)₂O₅, and 1 465 μg/g for REO, respectively. The iron–aluminum member of Benxi Formation in Yangquan Mining Area holds significant integrated exploration and development potential for critical metals such as Li, Ga, Zr, Nb, and REY.