Lithium–Cs–Ta-enriched (LCT-type) pegmatites are characterized by zoning texture and extreme enrichment of rare-metals. The role of fluids in zonation development and rare-metal mineralization remains a topic of debate. The Koktokay No. 3 pegmatite in northwestern China represents a typical LCT-type pegmatite characterized by economically significant Li–Be–Nb–Ta–Cs mineralization. This pegmatite exhibits a complete evolutionary sequence from outer to inner zones, with diverse rare-metal mineralization. Tourmaline is ubiquitously present in all textural zones of LCT-type pegmatites. In the Koktokay No. 3 pegmatite, the tourmalines exhibit a range of compositions from dravite and schorl to elbaite and rossmanite. The tourmalines in this pegmatite are characterized by significantly enriched light B isotope compositions (δ11B = −14.8‰ to −8.1‰), similar to those typically observed in most pegmatites derived from continental crust sources. The tourmalines in the outer zones have less variable δ11B values (−13.8‰ to −11.5‰) and are interpreted to have crystallized in a viscous magma. The tourmalines in the inner zones exhibit larger variations in δ11B values (−14.8‰ to −8.1‰) than those from the outer zones. The decreasing δ11B values of tourmalines from the outer to inner zones are attributed to the separation of an immiscible fluid phase that preferentially incorporated heavy B isotopes. The occurrence of hydrothermal tourmaline as veinlets indicates the exsolution of fluids in inner zones, with high δ11B values ranging from −10.2‰ to −9.3‰. Therefore, the hydrothermal fluid can be saturated when the magma has been strongly evolved. In addition to fractional crystallization, exsolved fluids play a significant role in the formation of internal zones and rare-metal mineralization in LCT-type pegmatites. The rare-metals are gradually enriched through fractional crystallization of magma, and the fluid contains mobile elements such as Cs that facilitate precipitation of rare-metal minerals.