Pegmatites occur widely in the Ke'eryin rare metal orefield. The genesis and evolution of the Ke'eryin pegmatites are still in dispute, and morphological and geochemical studies on tourmalines from the Ke'eryin pegmatites are limited. In this study, in-situ analyses of major and trace elements and B isotope were conducted to uncover the origin of tourmaline and the evolution of related pegmatites. Three types of tourmaline from the Ke'eryin barren pegmatite were identified: elongated columnar or needle-columnar tourmaline (Tur-1 type), isolated, disseminated, irregular, and massive tourmaline (Tur-2 type), and long columnar tourmaline (Tur-3 type). Petrographically, the Tur-1 type crystallized at the early stage of pegmatitic crystallization sequence, the Tur-2 type possibly formed at the early- and/or syn-pegmatitic crystallization sequence, whereas the Tur-3 type likely formed at the relatively late crystallization sequence. Compositionally, most tourmalines belong to the alkali group with a few falling in the vacancy group. All the tourmalines show a schorl composition and are of magmatic origin. Chemical variations from the Tur-1 to Tur-3 tourmalines are controlled by magma fractionation and melt compositions rather than crystal chemical effects. Most tourmalines follow the (Na, Mg)(Xvac, Al)−1, (Mg, OH)(Al, O)−1, and (Ca, Mg2)(Xvac, Al2)−1 exchange vectors. The higher contents of Zn, Sn, Li, Be, Nb, and Ta and negative Eu anomalies in the Tur-3 type indicate that it was likely crystallized at a more evolved stage. In combination with textural evidence and tourmaline chemistry, we suggest that the Tur-1 and Tur-2 types were formed at the relatively earlier stage of pegmatite-forming magma and the Tur-3 type was likely formed closer to the end-stage of barren pegmatite crystallization. The B isotopic compositions are relatively homogeneous and display slightly higher in the Tur-3 type, which were likely caused by fractional crystallization during B-rich magma evolution. It can be inferred that the tourmaline in more evolved and/or Li-mineralized pegmatite with magma evolution should have higher Li, Be, Nb, Ta, and Sn contents, implying that tourmaline chemistry may be used as a potential exploration indicator for rare metal mineralization.