Breadcrust bombs are pyroclasts displaying fractured, dense surfaces enveloping expanded interiors, and are associated with Vulcanian explosions. We document pyroclasts from the 2008–2009 CE eruption of Chaitén (Chile) that are internally as well as externally breadcrusted. The pyroclasts are cut by intersecting micrometer- to millimeter-thick tuffisites with dense glassy walls, which grade into strongly inflated pumiceous material. We find H2O diffusion gradients proximal to the breadcrusted surfaces, such that H2O is depleted from far-field magma (0.68 ± 0.04 wt%) into dense, fractured vein walls (0.2–0.3 wt%), indicating a spatial association between H2O mass transfer within the pyroclast interior and both suppressed vesiculation and breadcrusting. We experimentally confirm that diffusive H2O depletion suppresses bubble growth at shallow conduit conditions. Therefore, we interpret the breadcrust formation to be induced by H2O diffusion and the associated rise in viscosity rather than by cooling in the classical breadcrust-formation models. We posit that a “dehydration quench” is important as degassing continues to very low H2O contents in shallow-conduit magma that continues to vesiculate.