Explosive eruptions at basaltic volcanoes have been linked to gas segregation from magmas at shallow depths in the crust. The composition of primary melts formed at greater depths was thought to have little influence on eruptive style. Ocean island basaltic volcanoes are the product of melting of a geochemically heterogeneous mantle plume and are expected to give rise to heterogeneous primary melts. This range in primary melt composition, particularly with respect to the volatile components, will profoundly influence magma buoyancy, storage and eruption style. Here we analyse the geochemistry of a suite of melt inclusions from 25 historical eruptions at the ocean island volcano of Kīlauea, Hawai‘i, over the past 600 years. We find that more explosive styles of eruption at Kīlauea Volcano are associated statistically with more geochemically enriched primary melts that have higher volatile concentrations. These enriched melts ascend faster and retain their primary nature, undergoing little interaction with the magma reservoir at the volcano’s summit. We conclude that the eruption style and magma-supply rate at Kīlauea are fundamentally linked to the geochemistry of the primary melts formed deep below the volcano. Magmas might therefore be predisposed towards explosivity right at the point of formation in their mantle source region.