Arsenian pyrite in the Shuiyindong Carlin-type gold deposit in Guizhou, China, is the major host for gold with 300 to 4,000 ppm Au and 0.65 to 14.1 wt.% As. Electron miroprobe data show a negative correlation of As and S in arsenian pyrite, which is consistent with the substitution of As for S in the pyrite structure. The relatively homogeneous distribution of gold in arsenian pyrite and a positive correlation of As and Au, with Au/As ratios below the solubility limit of gold in arsenian pyrite, suggest that invisible gold is likely present as Au1+ in a structurally bound Au complex in arsenian pyrite. Geochemical modeling using the laser ablation-inductively coupled plasma mass spectrometry (LA-ICP-MS) analysis of fluid inclusions for the major ore forming stage shows that the dominant Au species were Au(HS)2− (77%) and AuHS(aq)0 (23%). Gold-hydroxyl and Gold-chloride complexes were negligible. The ore fluid was undersaturated with respect to native Au, with a saturation index of −3.8. The predominant As species was H3AsO30(aq). Pyrite in the Shuiyindong deposit shows chemical zonation with rims richer in As and Au than cores, reflecting the chemical evolution of the ore-bearing fluids. The early ore fluids had relatively high activities of As and Au, to deposit unzoned and zoned arsenian pyrite that host most gold in the deposit. The ore fluids then became depleted in Au and As and formed As-poor pyrite overgrowth rims on gold-bearing arsenian pyrite. Arsenopyrite overgrowth aggregates on arsenian pyrite indicate a late fluid with relatively high activity of As. The lack of evidence of boiling and the low iron content of fluid inclusions in quartz, suggest that iron in arsenian pyrite was most likely derived from dissolution of ferroan minerals in the host rocks, with sulfidation of the dissolved iron by H2S-rich ore fluids being the most important mechanism of gold deposition in the Shuiyindong Carlin-type deposit.