Abstract: The Gejiu tin polymetallic deposits are located in the southeastern part of Yunnan Province in China. A detailed electronic microprobe study has been carried out to document geochemical compositions of tourmalines from the deposits. The results indicate a systematic change of mineral geochemical compositions, which might be used as a mineral geochemical tracer for post-magmatic hydrothermal fluid, basin fluid and their mixture. The tourmalines from granite are schorl with Fe/(Fe+Mg) ratios of 0.912-1.00 and Na/(Na+Ca) ratios of 0.892-0.981. Tourmalines as an inclusion in quartz from the ore bodies are dravite with Fe/(Fe+Mg) ratios of 0.212-0.519 and Na/ (Na+Ca) ratios of 0.786-0.997. Tourmalines from the country rocks are dravite with Fe/(Fe+Mg) ratios of 0.313-0.337 and Na/(Na+Ca) ratio of 0.599-0.723. Tourmalines from cassiterite-tourmaline veins that occur in crannies within the country rocks show distinct optical zoning with alternate occurrence of dravite and schorl, Fe/(Fe+Mg)=0.374-0.843, Na/(Na+Ca)=0.538-0.987. It suggests that schorl in granite and dravite in carbonatite are related to magmatic fluid and basin fluid respectively. When magmatic fluid rose up and entered into crannies of the country rocks, consisting mainly of carbonatite, basin fluid would be constantly added to the magmatic fluid. The two types of fluid were mixed in structural crannies of the sedimentary basin accompanied with periodic geochemical oscillations to form material records in chemical composition zonings of tourmalines.