—We present results of geochemical and Sr–Nd isotope studies of rocks and of local dating and determination of the Lu–Hf isotope composition of zircons from late Vendian–early Cambrian and Cambrian–Ordovician intrusive associations (granitoids and gabbroids) of the Kaa-Khem and East Tannu-Ola batholiths in Eastern Tuva. The wide ranges of the eNd values (6.9 to 0.5) of rocks and the εHf values of magmatic and inherited zircons reflect the diversity of the magma sources of late Vendian–early Paleozoic intrusive associations formed at the island arc and accretion–collision stages. Late Vendian (572–562 Ma, Kopto and Buren massifs) and early Cambrian (522–518 Ma, East Tannu-Ola batholith) island arc tholeiitic and calc-alkalic plagiogranitoids resulted from the melting of the Vendian–early Cambrian island arc crust without the contribution of a more ancient crustal material. The subalkalic gabbro–monzodiorite–granosyenite association of the Zubovka massif (510 Ma) formed from a mantle source depleted isotopically but enriched in incompatible elements, with the participation of an island arc crust material; this process took place in the early phase of plume activity at the accretion–collision stage. Island arc complexes were the main source of Cambrian–Ordovician accretion–collision calc-alkalic plagiogranitoids (500–450 Ma, Terektyg-Cheder, Karaos, Tapsa, Baisyut, and other massifs). Variations in their composition were due to the melting of thick crust, whose isotopic heterogeneity was caused by the different contributions of a more ancient crustal source. The crust of the Tuva–Mongolian terrane made the main contribution to the formation of the potassic granitoids of the Bren’ massif (450 Ma), marking the completion of accretion–collision processes in this region. The isotope parameters of the Vendian–early Paleozoic granitoids are indicators of the crust formation and evolution in the course of subduction and accretion–collision processes.