The Jiajika rare metal deposit contains the largest area of granitic pegmatite-type rare metal deposits in China. The X03 vein is an immense rare metal deposit dominated by lithium, which was found in the deposit in recent years. The contact metamorphic belt of tourmalinization and petrochemistry is widely developed in its wall rocks, and the altered rocks formed contain Li and other rare metal mineralization. In this paper, the tourmaline found in the different rocks of the Jiajika X03 vein is divided into four types: two-mica quartz schist (Tur-Ⅰ), tourmaline hornfels (Tur-Ⅱ), tourmaline-bearing granite pegmatite (Tur-Ⅲ) and spodumene-bearing granite pegmatite (Tur-Ⅳ); their in situ major element, trace element and boron isotope data are systematically studied. The results show that all tourmalines in the Jiajika X03 vein deposit belong to the alkali group, and are schorl–Oxy/Fluor–schorl, dravite–Hydroxy-dravite and foitite–Oxy foitite solid solutions, among which Tur-Ⅰ are dravite, Tur-Ⅱ are foitite of hydrothermal origin and Tur-Ⅲ and Tur-Ⅳ are schorl of magmatic origin. The boron isotope values show that the boron involved the formation process of tourmaline mainly originates from the Majingzi S-type granite, and the boron isotope variations in tourmaline are controlled by melt fluid and Rayleigh fractionation. Moreover, there is a clear correlation between the B isotope value of tourmaline and the Li, Mn, Zn, Mg, and V contents, showing that these contents in tourmaline are good indicators of the mineralization type of pegmatite.