In most porphryr, systems the obscuring effects of hydrothermal processes and subsequent alteration, along with limited exposure of source rocks, preclude a detailed understanding of how and where metals and volatiles were derived. However, in this study we examine melt inclusions which have escaped alteration and that sampled all of the phases coexisting in the magma, in late- and postmineral rhyolitic units from the Rio Blanco Cu-Mo deposit, Chile. These inclusions demonstrate the existence of a volatile-rich melt, the exsolution from it of an aqueous volatile-rich phase, initially as melt + vapor bubble emulsions, and the disruption of these emulsions into melt and primary magmatic fluids. Trapping of these emulsions may explain the occurrence of melt inclusions containing widely, varying proportions of melt and aqueous fluid found at Rio Blanco. We demonstrate the sequestering of metals into the exsolved volatile phases and the derivation from these of possible ore-forming hydrothermal fluids, with particular reference to the implications for metal transport. Melt inclusions show differences between adjacent comagmatic intrusions that may be directly related to the extent of mineralization of the respective bodies. In one of the Rio Blanco postmineral rhyolite bodies melt inclusions show exsolution of the volatile-rich phase but only minor evidence of trapping of a metal-rich vapor. In contrast, inclusions from an adjacent late mineral rhyolite body show similar volatile phase exsolution but also provide evidence of ponding of metal-rich hydrothermal fluids during the final stages of cooling.