The rare potassium zirconium silicate dalyite has been identified for the first time on Terceira, Azores, within syenitic ejecta of the Caldeira-Castelinho Ignimbrite Formation. New quantitative analyses of this dalyite were combined with the small number of published analyses from various locations worldwide to evaluate the mineral's compositional variability. Additionally, solid-state modelling has been applied to assess the site allocations of substituting elements. The new analyses yield the average formula (K1.84Na0.15)∑=1.99(Zr0.94Ti0.012Hf0.011Fe0.004)∑=0.967Si6.03O15. Model results predict the placement of substituting Hf and Ti in the octahedral site, and highlight the overall complexity in the incorporation of Fe, Mg and Ba. The combined dataset reveals that dalyite found within peralkaline granites and syenites is generally defined by higher Na↔K substitution and lower Ti↔Zr substitution relative to dalyite from highly potassic rocks. The Terceira dalyite exhibits a bimodal variation in the degree of Na↔K substitution which is attributed to a K-enrichment trend induced by late-stage pore wall crystallization and albitization, coupled with the control of pore size upon the degree of supersaturation required to initiate nucleation of dalyite in pores of varying size.