Voluminous basalts dominate a middle Tertiary bimodal volcanic assemblage in the Queen Charlotte Islands, British Columbia, Canada. These moderately enriched mid-ocean-ridge basalt (MORB-)like magmas were associated with significant crustal extension related to the subduction of the Pacific–Farallon ridge and the initiation of a slab window environment, which persisted for 35 Ma. These asthenospheric melts were derived from a low degree of melting of a heterogeneous peridotite source mainly in the spinel stability field, as inferred from fractional melting inversion calculations. The basaltic magmas in turn gave rise to both tholeiitic and calc-alkaline volcanic strata up to 3.5 km thick in local grabens. The tholeiitic basalts resemble MORB, with rare-earth element (REE) patterns ranging from slightly depleted to enriched in light REE (LREE). The calc-alkaline basaltic andesites are enriched in LREE, but are not strongly depleted in Nb. The rocks have overlapping Nd, Sr, and Pb isotopic compositions, similar to those of intraplate basalts from the adjacent northeast Pacific seamounts and Cordillera. The difference between the tholeiitic and calc-alkaline rocks is, in part, attributed to polybaric fractional crystallization of different proportions of plagioclase to mafic minerals from a similar tholeiitic magma. This marginal-basin subalkaline volcanic sequence and its genesis describe the slab window environment for the Tertiary tectonics of the western Canadian continental margin and provide a model for older combined tholeiitic and calc-alkaline volcanic successions.