Reconstructing the thermal evolution of hydrothermal ore deposits mainly relies on their fluid inclusion record, which is limited by favorable trapping conditions, calling for alternative temperature constraints. Muscovite and tourmaline coexist in many hydrothermal ore deposits and in the granites or pegmatites related with them. Whereas in situ analyses of boron isotopes in tourmaline are widely applied to constrain fluid sources and evolution, muscovite has seldom been used in this way, and the potential for isotope exchange thermometry with this mineral pair is unexplored. The different boron coordination in muscovite and tourmaline causes a significant, temperature-dependent isotopic fractionation between them, which has been determined experimentally. We used this relationship to study mineralization conditions and fluid evolution at the Panasqueira W-Sn-Cu deposit in Portugal, where the source and evolution of the mineralizing fluids are still debated. The difference in 11B/10B ratios of coexisting muscovite and tourmaline, expressed as Δ11Bmica-tourmaline = δ11Bmica –δ11Btourmaline, yields median temperatures for vein selvages from 400° to 460°C within a total range of 350° to 600°C, which agrees with published Ti-in-quartz temperatures. Mineral pairs from a late fault zone yield a lower median temperature of about 250°C (range 220°–320°C), which fits with published homogenization temperatures of quartz-hosted fluid inclusions from the veins. Taking these temperatures into account, the calculated fluid composition of the early and late muscovite generations is about δ11Bfluid = −6 ± 2‰, which indicates that the recurrent fluid pulses had a uniform composition and a magmatic-hydrothermal origin.