Mineralised igneous complexes of Ordovician age from New South Wales range in composition from quartz-rich medium-K dacites (e.g. Copper Hill), to quartz-poor, high-K to 'shoshonitic' monzodioritic to monzonitic complexes (Goonumbla and Cadia). Despite Ordovician igneous suites being considered mostly 'shoshonitic' by some authors, only the Cadia Igneous Complex is potassic in the sense of having molecular K/ Na greater than unity. A feature of the intrusive complexes is that each is spatially associated with volcanic rocks of similar compositional character, and that these relationships may occur over long periods of time within local regions (e.g. Goonumbla Volcanic Complex), or show progressive compositional evolution over probably shorter time periods as in the case of the Cadia District. The igneous suites are variably enriched in K and LILE elements, with uniformly high K/Rb ratios, low mantle-compatible element abundances and marked depletions in Ti, Nb and Ta, which is consistent with a subduction-related tectonic setting. Patterns of enrichment and depletion between each suite are similar, and are consistent with the magmas having been derived from sources variably enriched by slab derived materials prior to fusion. Recent dating results from the Goonumbla Volcanic Complex suggest that this enrichment was not progressive over time, and that the oldest intrusions in the Ordovician are not necessarily the least compositionally evolved. These results confirm the overall 'calcalkaline' nature of Ordovician magmatism and do not support models that argue against contemporaneous subduction on the grounds that Ordovician magmatism was almost exclusively shoshonitic in character. Economic size and significance of associated deposits increase with the degree of K-enrichment (but not total alkali contents) observed in the associated igneous complexes, and supports conceptual models that link mineralisation potential and fertility with processes related to the production of K-enriched protoliths.