Orthogneisses of late-Hercynian protolith age crop out in the Central Rhodope high-grade metamorphic complex, which is part of the Alpine orogen in south-eastern Europe. They compose a tectonic unit bordered by late-Alpine extensional shear zones. These rocks reflect Eocene amphibolite facies migmatization (<750 °C/0.9–0.5 GPa). The low-temperature melting favored zircon inheritance and disturbed mainly the LILE protolith compositions. Despite the intense Alpine metamorphic overprint, the major elements, HFSE and REE reflect the initial composition of the Hercynian protolith. A geochemical data set summarizing 200 whole rock analyses testifies to a calc-alkaline magma differentiation producing a compositional range of tonalite and/or granodiorite to granite and leucocratic granite. Geochemical compositions combined with published isotope and age data suggest dominant I-type protoliths and mixed magma sources including crustal and mantle material, and distinguish between older granitoids of volcanic-arc affinity and probably younger ones of late or post-collision origin.