The provenance and depositional setting of Late Palaeozoic and Early Mesozoic clastic sediments from the eastern Aegean archipelago are examined here for the first time using whole-rock geochemistry and composition of detrital chrome spinel. Major- and trace-element data for Late Palaeozoic and Permo-Triassic clastic sediments from the Lower and Upper Units of Chios are compatible with an acidic to intermediate source, minor input of (ultra)mafic detritus and recycling of older sedimentary components. Chondrite-normalized REE profiles are uniform with light REE enrichments (LaN/YbNc. 7.7), negative Eu anomalies (Eu/Eu* c. 0.67) and flat heavy REE patterns (GdN/YbNc. 1.5), indicating an upper continental crustal source and/or young differentiated arc material. Detrital chrome spinel from the clastic sediments of Chios has Cr-number (Cr/(Cr + Al)) values between 0.29 and 0.89 and Mg-number (Mg/(Mg + Fe2+)) values between 0.24 and 0.70, suggesting a probably mixed (ultra)mafic source involving ridge peridotites (mid-ocean ridge type), fore-arc peridotites and island-arc basalts. The metasediments from the islands of Inousses and Psara have similar whole-rock chemical signatures to those of Chios, although no evidence was found for an (ultra)mafic source. We conclude that both the Late Palaeozoic sediments from the Lower and Upper Units of Chios and the metasediments from Inousses and Psara were deposited in a continental island-arc setting until at least Late Permian times, probably at a single Palaeotethyan margin. They are interpreted to be allochthonous, tectonically transported to their present position by Late Mesozoic to Cenozoic orogenic processes.