Field, geochemical, and geochronologic data of high-grade basement metamafic and evolved rocks are used to identify the nature and timing of pre-Alpine crustal growth of the Rhodope Massif. These rocks occur intrusive into clastic-carbonate metasedimentary succession. Petrography and mineral chemistry show compositions consistent with Alpine amphibolite-facies metamorphism that obliterated the original igneous textures of the protoliths. Bulk-rock geochemistry identifies low-Ti tholeiitic to calc-alkaline gabbroic-basaltic and plagiogranite precursors, with MORB-IAT supra-subduction zone signature and trace elements comparable to modern back-arc basalts. The U-Pb zircon dating revealed a mean age of 455 Ma for the magmatic crystallization of the protoliths that contain inherited Cambrian (528–534 Ma) zircons. Carboniferous, Jurassic, and Eocene metamorphic events overprinted the Ordovician protoliths. The radiometric results of the metamorphic rocks demonstrate that Ordovician oceanic crust was involved in the build-up of the Rhodope high-grade basement. Dating of Eocene-Oligocene volcanic rocks overlying or cross-cutting the metamorphic rocks supplied Neoproterozoic, Ordovician and Permo-Carboniferous xenocrystic zircons that were sampled en route to the surface from the basement. The volcanic rocks thus confirm sub-regionally present Neoproterozoic and Paleozoic igneous and metamorphic basement. We interpret the origin of the Middle-Late Ordovician oceanic magmatism in a back-arc rift-spreading center propagating along peri-Gondwanan Cadomian basement terrane related to the Rheic Ocean widening. The results highlight the presence of elements of Cadomian northern Gondwana margin in the high-grade basement and record of Rheic Ocean evolution. The eastern Rhodope Massif high-grade basement compared to adjacent terranes with Neoproterozoic and Cambro-Ordovician evolution shares analogous tectono-magmatic record providing a linkage among basement terranes incorporated in the Alpine belt of the north Aegean region.