The attributes of Late Paleozoic magmatic events are of paramount significance in elucidating the tectonic evolution of the Ulanhot region, which is located in the middle of the Hegenshan–Heihe tectonic belt (HHTB). This study undertook a comprehensive investigation of the petrography, LA–ICP–MS zircon U–Pb dating, whole rock geochemistry, and zircon Hf isotopes of the Early Carboniferous volcanic rocks. The volcanic rocks are predominantly composed of andesite, schist (which protolith is rhyolitic tuff), and rhyolitic tuff. The results of zircon U–Pb dating reveal that the formation ages of volcanic rocks are Early Carboniferous (343–347.4 Ma). Geochemical characteristics indicate that the andesites possess a comparatively elevated concentration of Al₂O₃, alongside diminished levels of MgO and TiO₂, belonging to the high-K calc-alkaline series. The zircon εHf(t) of the andesites range from −13 to 9.4, while the two-stage Hf model ages span from 697 to 1937 Ma. The felsic volcanic rocks have high contents of SiO₂ and Na₂O + K₂O, low contents of MgO and TiO₂, and belong to high-K to normal calc-alkaline series. The zircon εHf(t) values of the felsic volcanic rocks range from −12.8 to 10, while the two-stage Hf model ages span from 693 to 2158 Ma. The Early Carboniferous volcanic rocks exhibit a notable enrichment in large ion lithophile elements (LILEs, such as Rb, K, Ba) and light rare earth elements (LREEs), depletion in high-field-strength elements (HFSEs, including Nb, Ta, Ti, Hf), as well as heavy rare earth elements (HREEs). The distribution patterns of the rare earth elements (REEs) demonstrate a conspicuous right-leaning tendency, accompanied by weak negative Eu anomalies. These characteristics indicate that the andesites represent products of multistage mixing and interaction between crustal and mantle materials in a subduction zone setting. The felsic volcanic rocks originated from the partial melting of crustal materials. Early Carboniferous igneous rocks formed in a volcanic arc setting are characteristic of an active continental margin. The identification of Early Carboniferous arc volcanic rocks in the Central Great Xing’an Range suggests that this region was under the subduction background of the oceanic plate subduction before the collision and amalgamation of the Erguna–Xing’an Block and the Songnen Block in the Early Carboniferous.