The Xiangzhong metallogenic province (XZMP), the largest polymetallic mineralization province in southern China, is known for its large number of Sb and Sb-polymetallic deposits (>100). In this study, detailed microscope observation, trace element, and sulfur isotopic analyses were performed on stibnite from the Xikuangshan, Woxi, and Banxi deposits in the XZMP to constrain the ore genesis.Stibnite from three deposits appears similar under backscattered electron imaging and has similar major elements contents. Detectable trace elements in stibnite are Fe, Cu, Zn, As, and Pb. Base metals (Cu, Pb, and Zn) are enriched in stibnite from the Woxi deposit but are depleted in stibnite from the Xikuangshan and Banxi deposits. Gold is detectable only in stibnite from the Woxi deposit. Cu, As, and Pb mainly occur as solid solutions within the crystal lattice in stibnite, while micro-scale inclusions of Fe- and/or Zn-rich phases are also observed. The δ34S values of stibnite from three deposits are distinct but with narrow ranges: +6.8 to +10.2 ‰; +5.5 to +6.5 ‰; −4.2 to +0.1 ‰ for the Xikuangshan, Banxi, and Woxi deposits, respectively. The δ34S values of stibnite suggest that the underlying basement rocks are the potential source of sulfur for the Sb mineralization in the Xikuangshan and Banxi districts while sulfur for the Sb mineralization of the Woxi district may have originated from a deep magmatic source. In addition, a positive trend between the δ34S values of stibnite and sampling depth suggests an input of the 34S-rich basin brine during the mineralization in the Woxi district.We propose a genetic model for the Sb mineralization in the XZMP: Fluids rich in Sb, Au, W, Cu, Pb, and Zn related to igneous activities ascended via regional deep faults and mixed with 34S-rich basin brine. Ore minerals of Sb, Au, and W were deposited within structural traps resulting in the Woxi-type deposits. The basement-derived deep fluids driven by orogenic leached Sb and related metals from the basement metamorphic rocks, which migrated via the regional faults and mixed with cold near surface meteoric water to form the Xikuangshan-type deposits.