This paper explores the role of melt fracturing in degassing rhyolitic volcanic systems. The Monte Pilato-Rocche Rosse eruptions in Italy evolved from explosive to effusive in style, and H₂O content in quenched glasses changed over time from relatively H₂O-rich (~ 0.90 wt.%) to H₂O-poor dense obsidian (~ 0.10–0.20 wt.%). In addition, healed fractures have been recorded in all different eruptive materials, from the glass of early-erupted tube pumice and rinds of breadcrusted obsidian pyroclasts, to the glass of late-erupted dense obsidian pyroclasts, and throughout the final effusive Rocche Rosse lava flow. These rocks show multiple fault sets, some with crenulated fault planes indicating resumption of viscous flow after faulting, complex obsidian breccias with evidence for post-brecciation folding and stretching, and centimetre- to metre-thick tuffisite preserved in pyroclasts and lava, representing collapsed foam due to fracturing of vesicle walls. These microstructural observations indicate that multiple fracturing and healing events occurred during both explosive and effusive eruptions. H₂O content in glass decreases by as much as 0.14 wt.% towards healed fractures/faults and decreases in stretched obsidian breccias towards regions of intense brecciation. A drop in pressure and/or increase in temperature along fractures caused diffusive H₂O migration through melt towards fracture surfaces. Repetitive and pervasive fracturing and healing thereby create conditions for diffusive H₂O loss into fractures and subsequent escape through permeable paths. This type of progressive magma degassing provides a potential mechanism to explain the formation of dense obsidian and the evolution from explosive to effusive eruption style.