Abstract The Rhodiani ophiolites are represented by two tectonically superimposed ophiolitic units: the “lower” Ultramafic unit and the “upper” Volcanic unit, both bearing calcareous sedimentary covers. The Ultramafic unit consists of mantle harzburgites with dunite pods and chromitite ores, and represents the typical mantle section of supra-subduction zone (SSZ) settings. The Volcanic unit is represented by a sheeted dyke complex overlain by a pillow and massive lava sequence, both including basalts, basaltic andesites, andesites, and dacites. Chemically, the Volcanic unit displays low-Ti affinity typical of island arc tholeiite (IAT) ophiolitic series from SSZ settings, having, as most distinctive chemical features, low Ti/V ratios (< 20) and depletion in high field strength elements and light rare earth elements. The rare earth element and incompatible element composition of the more primitive basaltic andesites from the Rhodiani ophiolites can be successfully reproduced with about 15% non-modal fractional melting of depleted lherzolites, which are very common in the Hellenide ophiolites. The calculated residua correspond to the depleted harzburgites found in the Rhodiani and Othrys ophiolites. Both field and chemical evidence suggest that the whole sequence of the Rhodiani Volcanic unit (from basalt to dacite) originated by low-pressure fractional crystallization under partially open-system conditions. The modelling of mantle source, melt generation, and mantle residua carried out in this paper provides new constraints for the tectono-magmatic evolution of the Mirdita–Pindos oceanic basin.