Frances Adamson will step down as departmental secretary of Foreign Affairs and Trade to become governor of South Australia in October.
Ms Adamson will step down from DFAT on June 25.
SA Premier Steven Marshall made the announcement on Tuesday following the Queen's approval of the appointment as her representative in the state.
Ms Adamson will become the state's 36th governor, succeeding Hieu Van Le, who has served for in the role for seven years.
"I am greatly looking forward to returning home to serve the people of South Australia and contribute to the state's international engagement through the promotion of trade, investment and people-to-people links," Ms Adamson said.
"I feel privileged to be succeeding His Excellency the Honourable Hieu Van Le AC, who has served with such distinction."
Mr Marshall said the appointment represents a new era for the state, which has global ambitions.
"She is a very proud South Australian with a plethora of experience in international affairs - vitally important to South Australia as we recover from the once-in-a-century COVID-19 pandemic," he said in a statement.
"Her wealth of knowledge on the international stage will put South Australia in good stead as we continue to put South Australia on the global map."
Foreign Affairs Minister Marise Payne paid tribute to Ms Adamson's "distinguished career", particularly her oversight of the 2017 foreign policy white paper.
"Ms Adamson has led the department ably during a period of considerable strategic challenge, including leading implementation of the Pacific Step-up; enhanced engagement in south-east Asia; and a reorientation of the aid program towards regional recovery from COVID-19," Senator Payne said in a statement.
"Under her leadership, the department has undertaken the largest consular operation in DFAT's history in response to the global COVID-19 pandemic. During this critical time, Ms Adamson's support to her staff, including those posted overseas, has enabled them to provide continuing assistance to Australians abroad.
"Within the department, Ms Adamson has championed ambitious internal reform, including a highly successful Women in Leadership program, and a strengthened focus on diversity and inclusion. Her intellect and experience are respected across government, business and the broader community."
Ms Adamson has led DFAT since 2016, following a diplomatic career that took her to Beijing as Australia's ambassador to China, London as deputy high commissioner, as well as postings in Hong Kong and Taipei.
The daughter of former South Australian Liberal MP Jennifer Cashmore, Ms Adamson went on to work as chief of staff to ministers for defence and foreign affairs and served as prime minister Malcolm Turnbull's foreign policy adviser.
She is married to Rod Bunten and they have four adult children.
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