The selection of Masoomeh Ebtekar as vice president for environmental affairs marks the second woman named to Rouhani's panel of vice presidents.
Ebtekar was also vice president under reformist President Mohammad Khatami from 1997-2005.
Ebteker, who is fluent in English, was a main spokeswoman during the 444-day hostage standoff. She later served on the Tehran Municipal Council and became a respected scholar in environmental studies.
The official IRNA news agency also said Rouhani today named a former defense minister, Adm Ali Shamkhani, to lead the Supreme National Security Council.
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