Bimodal associations of basalt and rhyolite of Upper Ordovician age which were erupted in a submarine environment occur within the Caledonian orogenic belt of South Britain at Parys Mountain (Anglesey), in Snowdonia (North Wales) and at Avoca (SE Ireland). The volcanic rocks have experienced hydrothermal alteration and low-grade metamorphism, and therefore immobile elements (e.g. Ti, Zr, Nb, Y) have been used to identify the original geochemical characteristics. The basalts have characters transitional between volcanic ‘arc’ and ‘within plate’ types consistent with eruption on an extensional part of an active continental margin. Two groups of rhyolites have been identified. A low-Zr group (Zr<500ppm), represented at all three locations, is interpreted as originally of high-K, subalkaline type. A high-Zr group (Zr>500ppm), represented at Snowdonia and Avoca, is interpreted as originally being peralkaline in composition; their high Zr/Nb ratios (>10) are typical of peralkaline rhyolites erupted above subduction zones. The bimodal nature of the associations and the peralkaline character of some rhyolites indicates magma production in a complex tectonic setting, transitional between an active continental margin/island arc and an extensional environment. Associated sulphide mineralization is volcanogenic and probably syn-sedimentary. High-level, rhyolitic magma chambers are thought to have driven convection of the hydrothermal fluids from which the sulphides precipitated.