The Napo-Qinzhou Tectonic Belt (NQTB) lies at the junction of the Yangtze, Cathaysia and Indochina (North Vietnam) Blocks, which is composed of five major lithotectonic subunits: the Qinzhou-Fangcheng Suture Zone (QFSZ), the Shiwandashan Basin (SB), the Pingxiang-Nanning Suture Zone (PNSZ), the Damingshan Block (DB) and the Babu-Lingma Suture Zone (BLSZ). On the basis of geochemical compositions, the Permian mafic igneous rocks can be divided into three distinct groups: (1) mafic igneous rocks (Group 1) from the Longjing region in the PNSZ and Hurun region in the BLSZ, which are characterized by intermediate Ti, P and Zr with low Ni and Cr contents; (2) mafic igneous rocks (Group 2) from the Naxiao and Chongzuo region in the DB, characterized by low-intermediate Ti, P and Zr with high Ni and Cr concentrations; and (3) mafic igneous rocks (Group 3) from the Siming region in the Jingxi carbonate platform of the northwestern margin of the NQTB, with intermediate-high Ti, P and Zr and low Ni and Cr contents. The Group 1 rocks yield a weighted mean 206Pb/238U age of 250.5±2.8 Ma and are geochemically similar to basalts occurring in back-arc basin settings. The Group 2 rocks exhibit geochemical features to those basalts in island arcs, whereas the Group 3 rocks show geochemical similarity to that of ocean island basalts. All three groups are characterized by relatively low εNd(t) values (–2.61 to +1.10) and high initial 87Sr/86Sr isotopic ratios (0.705309–0.707434), indicating that they were derived from a subduction-modified lithospheric mantle and experienced assimilation, fractional crystallization, and crustal contamination or mixing during magmatic evolution. Accordingly, we propose the existence of an arc-back arc basin system that developed along the NQTB at the border of SW Guangxi Province (SW China) and northern Vietnam, and it was formed by continued northwestward subduction of the Cathaysian (or Yunkai) Block under the Yangtze Block, and northeastward subduction of the Indochina Block beneath the Yangtze Block during Permian time.