The world-class Huize deposit hosts significant germanium (Ge) resources in the Sichuan–Yunan–Guizhou (SYG) Mississippi Valley-type (MVT) Pb–Zn province of China. The distribution and enrichment mechanism of Ge is still poorly understood. In the main ore-forming stage of Huize, we identified six sphalerite colors from C1 (black) to C6 (white) in transmitted light. Two color sequences are confirmed, including C1 → C2 → C3 → C6 and C1 → C2 → C4 → C5 → C6. We used multiple analytical methods to reveal the Ge distribution and incorporation mechanism into sphalerite and the possible enrichment factors. Our results show that Ge occurs as argutite (GeO₂), and in the sphalerite crystal lattice, C1 and C3 sphalerite has up to 593 ppm Ge. Two substitution mechanisms, i.e., Ge⁴⁺ + □_(vacancy) → 2Zn²⁺ (e.g., C1 and C2) and Ge⁴⁺ + 2Cu⁺ → 3Zn²⁺ (e.g., C2, C3, C4, and C5), are inferred from the Huize sphalerite. They show different spatial structures of sphalerite and a weak shift of the white line observed by high-resolution X-ray absorption near-edge structure (XANES) spectroscopy. The trace-element composition of sphalerite suggests that reduced sulfur content of the ore-forming fluid contributes to Ge enrichment, followed by high temperature (> 300 °C).