In Central Galicia, there are occurrences of barren and Li–Sn–Ta-bearing pegmatites hosted by metasedimentary rocks. A number of common and contrasting features between Panceiros pegmatites (barren) and Li–Sn–Ta mineralized Presqueira pegmatite are established in this study. K-feldspar and muscovite have the same trace elements (Rb, Cs, P, Zn, and Ba), but the mineralized one has the highest Rb and Cs and the lowest P contents. The barren bodies show fluorapatite and eosphorite–childrenite replacing early silicates. The mineralized body has primary phosphates (fluorapatite and montebrasite), a metasomatic paragenesis (fluorapatite and goyazite) replacing early silicates, and a late hydrothermal assemblage (vivianite and messelite). Ta–Nb oxides from the Presqueira body show a trend from columbite-(Fe) to tantalite-(Fe) and tapiolite-(Fe). In this body, the Li-aluminosilicate textures support primary crystallization of petalite that was partially transformed into Spodumene + Quartz (SQI) during cooling, and into myrmekite during a Na-metasomatism stage. As a result of both processes, spodumene formed. The geochemical study supports magmatic differentiation increasing from the neighboring granites to the Li–Sn–Ta mineralized pegmatite. In both barren and mineralized bodies, the pegmatite-derived fluids that migrated into the wallrock were enriched in B, F, Li, Rb, and Cs and, moreover, in Sn, Zn, and As.