Early Cretaceous volcanic rocks are widely developed in the Longzi area, southern Tibet. Their petrogenesis and tectonic setting are important for understanding the initial breakup of eastern Gondwana and its deep geodynamic mechanisms. This study integrates field observations, petrography, zircon U-Pb geochronology and trace elements, whole-rock major and trace element geochemistry, and Sr-Nd-Pb isotopes to investigate the origin and tectonic significance of these rocks. The analyzed suite comprises diabase and rhyolite, with no intermediate compositions in the studied samples, thus defining a mafic–felsic volcanic association. Zircon U-Pb ages indicate Early Cretaceous magmatism at 132–138 Ma for the diabase and 132–134 Ma for the rhyolite. Geochemically, the mafic rocks are enriched in LREEs and HFSEs and display OIB-like trace-element characteristics, with ε_Nd(t) values ranging from −0.2 to +4.4, indicating derivation from low-degree partial melting of a spinel–garnet lherzolite source modified by limited interaction with the lithospheric mantle. The felsic rocks show pronounced negative Eu anomalies, A-type granite affinities, and ε_Nd(t) values ranging from −12.2 to −11.9, indicating derivation mainly from partial melting of upper-crustal materials. The marked geochemical and isotopic contrast between the mafic and felsic rocks argues against simple fractional crystallization from a common parental magma. Combined with regional geological data, these results indicate that the Longzi mafic–felsic volcanic association formed in an intraplate extensional setting related to Kerguelen-plume thermal input during the initial breakup of eastern Gondwana.