The Sichuan–Yunnan–Guizhou Pb-Zn metallogenic belt (SYG metallogenic belt), a crucial metallogenic unit on the southwestern margin of the Yangtze Block, is a key part of the South China low-temperature metallogenic domain. The incorporation mechanisms and distribution of trace elements (e.g., Ge, Ga, Cd) widely enriched in Pb-Zn sulfides throughout this region remain poorly understood. This study investigates main-ore-stage sulfides (sphalerite and pyrite) from the Maoping Pb-Zn deposit using in situ laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) analyses and mapping to systematically elucidate the partitioning and occurrence of these trace elements. The key findings are as follows: (1) Sulfides show distinct elemental partitioning: sphalerite preferentially concentrates Cd, Ag, Ge, Ga, and Se, whereas pyrite is significantly enriched in Mn, Ni, As, and Co. (2) Sphalerite is the primary host for many trace elements. Cadmium, Ge, Mn, Cu, and Ag mainly enter the sphalerite lattice by substituting for Zn²⁺. Coupled substitution mechanisms, such as Zn²⁺ ↔ Cd²⁺, 2Zn²⁺ ↔ Ge²⁺ + Cu²⁺, and 2Zn²⁺ ↔ Ga³⁺ + Cu⁺, facilitate the incorporation of Ge and Ga. (3) The sphalerite exhibits a trace element assemblage of high Cd-Ge and low Fe-Mn, which is geochemically similar to typical Mississippi Valley-type (MVT) deposits and differs significantly from sedimentary exhalative (SEDEX) and magmatic–hydrothermal deposits, indicating a medium- to low-temperature metallogenic environment. Based on these geochemical signatures and epigenetic textures, we confirm that the Maoping Pb-Zn deposit exhibits similarities with MVT deposits. Nevertheless, distinct differences in the tectonic setting and metal grades suggest it is a unique SYG-type Pb-Zn deposit.