Brittle fragmentation, generating small pyroclasts from magma, is a key process determining eruptive style. How low-viscosity magma fragments within a rising fountain in a brittle manner, however, is not well understood. Here we describe a fragmentation process in Hawaiian fountains on the basis of observations from the 2018 lower East Rift Zone eruption of Kīlauea Volcano, Hawai’i. The dominant fragmentation mechanism is inertia driven and produces a population of large fluidal pyroclasts. However, when sufficient volcanic gas is released in the fountain, a subpopulation of smaller and more vesicular pyroclasts is generated and entrained into the gas-dominant convective plume. The size distribution of these pyroclasts is similar to that of brittlely fragmented solid materials. The erupted high-vesicularity pyroclasts sometimes preserve a deformed shape. These observations suggest that late-stage rapid expansion lowers the gas temperature adiabatically and cools the outer surface of liquid pyroclasts below the glass transition temperature. The rigid crust fragments as the hot interior attempts to expand due to further volatile diffusion from the melt into bubbles. Adiabatic expansion of volcanic gas occurs in all eruptions. Brittle fragmentation induced by rapid adiabatic cooling may be a widespread process, although of varying importance, in explosive eruptions.