We present new data on the age, composition, and environments of formation of granites of the Kystarys complex and the associated Li-rich rare-element pegmatites of the South Sangilen pegmatite belt including the large Tastyg lithium deposit. It has been established that they formed during the Early Paleozoic collisional orogeny in the Tuva–Mongolian massif at the Cambrian–Ordovician boundary. The granites of the Kystarys complex are moderately alkaline high-K rocks and are enriched in Zr, Nb, Y, and REE; therefore, they are classified as postcollisional, transitional to within-plate (A-type). The spodumene pegmatites of the South Sangilen pegmatite belt are similar to the above granites in age and isotopic and geochemical parameters, which suggests a paragenetic relationship between these rocks. Pegmatites form several pegmatite fields within the belt, which differ in trace-element signatures. In addition to predominant Li, Cs, and Ta, specific to all spodumene pegmatites (LCT family), pegmatites of two fields have high contents of Nb, Y, REE, and Zr, which are indicator elements of NYF family pegmatites. It has been established that the formation of spodumene pegmatites with combined LCT–NYF geochemical signatures was preceded by the intrusion of dikes of monzogabbro with the geochemical characteristics of OIB and of alkali aegirine granites and by the formation of associated metasomatites enriched in Zr, Nb, Y, and REE. Based on the geological, mineralogical, and geochemical data, we substantiate the hypothesis of the formation of Li-bearing granite–pegmatite melts from a mixed source resulted from the influence of fluids of an alkaline igneous complex of mantle genesis on the crustal protolith.