Prime Minister Anthony Albanese on Monday announced former premier Jay Weatherill was appointed to the role, describing the choice as "entirely appropriate".
Mr Weatherill led the state between 2011 and 2018, and served in the SA parliament for 16 years, where he drove debate on defence capability, renewable energy targets and environmental protection issues.
Mr Albanese praised the former Labor premier as a leader in defence industry and as being "instrumental" in the construction of submarines.
"Jay is well placed to take forward AUKUS in our nation's interest, particularly with SSN-AUKUS, which we'll be doing in partnership with the United Kingdom," he said.
Under the AUKUS security pact with the US and UK, Australia will acquire nuclear-powered submarines.
The SSN-AUKUS class will be built in Adelaide, based on a British design, with the first to be completed in the early 2040s.
Former defence minister Stephen Smith is the outgoing high commissioner and has been in the role since January 2023.
The prime minister thanked him for his service and noted his leadership in Australia's work with the Coalition of the Willing, a group dedicated to strengthening Ukraine's defence against Russia's war.
"Stephen has done a remarkable job in representing Australia's interests across the UK, across security and defence matters in particular, he said.
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