We investigated the distribution of Cl, F, Li, and Be in pumices, obsidians, and crystallized dome rocks at Chaitén volcano in 2008–2009 in order to explore the behavior of these elements during explosive and effusive volcanic activity. Electron and ion microprobe analyses of matrix and inclusion glasses from pumice, obsidian, and microlite-rich dome rock indicate that Cl and other elements were lost primarily during crystallization of the rhyolitic dome after it had approached the surface. Glass in pumice and microlite-free obsidian has 888 ± 121 ppm Cl, whereas residual glass in evolved microlite-rich dome rock generally retains less Cl (as low as <100 ppm). Estimated Cl losses were likely >0.7 Mt Cl, with a potential maximum of 1.8 Mt for the entire 0.8-km³ dome. Elemental variations reflect an integrated bulk distribution ratio for Cl > 1.7 (1.7 times more Cl was degassed or incorporated into crystals than remained in the melt). Because Cl is lost dominantly as the very last H₂O is degassed, and Cl is minimally (if at all) partitioned into microlites, the integrated vapor/melt distribution ratio for Cl exceeds 200 (200 times more Cl in the evolved vapor than in the melt). Cl is likely lost as HCl, which is readily partitioned into magmatic vapor at low pressure. Cl loss is accelerated by the change in the composition of the residual melt due to microlite growth. Cl loss also may be affected by open-system gas fluxing. Integrated vapor-melt distribution ratios for Li, F, and Be all exceed 1,000. On degassing, an unknown fraction of these volatiles could be immediately dissolved in rainwater.