Anthony Albanese will attend the May 6 coronation of King Charles III in London.
The prime minister will be accompanied by Governor-General David Hurley and all of the state governors at the historic event.
"A number of other notable Australians, most of which are based in the United Kingdom, have been chosen to show the world the best of our values - caring for others, serving the community and championing progress," Mr Albanese told parliament on Thursday.
"And I note that the palace requested in particular that there be significant representation from Indigenous Australians as part of the coronation."
Defence force representatives will also attend.
Mr Albanese said he would hold talks with British prime minister Rishi Sunak on defence and trade, noting the Australia-UK free trade agreement received royal assent in the UK on March 23.
He will also visit the submarine yards in the port town of Barrow-in-Furness, following on from the agreement reached with the US and UK on building nuclear-powered submarines.