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Ionization of xenon atoms in single highly excited states ‖nf≳ (where 25⩽n⩽40) by collisions with CCl4, CCl3F, and SF6 has been investigated. Absolute rate constants for Xe+ production are reported together with the identities of the major negatively charged species produced in the collisions. Cross sections determined from these rate constants are also given. The data lend support to the theoretical model, which views such collisions as being dominated by the interaction between the target molecules and the excited electron, with the Xe+ ion core playing a minor role.