Mr Le, the current deputy, will replace Rear Admiral Kevin Scarce from September.
Premier Jay Weatherill said Mr Le had a great life story, having arrived in Australia from war-torn Vietnam as a refugee 36 years ago.
"[He is] the first Asian migrant to rise to the position of governor in our state's history," Mr Weatherill said.
"He has already demonstrated an outstanding level of service to the community and I have no doubt that he will serve the role with great distinction, as he has done in the role of Lieutenant-Governor since 2007."
Hieu Van Le AO
- Now 60, he was born in Quang Tri in central Vietnam in 1954
- He is married to Lan, who arrived with him on a boat from Vietnam 36 years ago
- They have two sons, Don and Kim, who they named after Australian cricketers Don Bradman and Kim Hughes
- Mr Le holds a degree in economics and accountancy and a Masters Degree in Business Administration from Adelaide University
- He is a member of the Certified Practising Accountants and from 1991 was a senior manager of the Australian Securities and Investments Commission until he retired in early 2009
- He is a patron and member of more than 30 community organisations
- Mr Le was appointed as an Officer in the Order of Australia on Australia Day in 2010
- He has been awarded the Australia Day Medal for outstanding service to the Australian Securities and Investments Commission
- He holds the Australian Centenary Medal 'for service to the advancement of multiculturalism in Australia'
- Adelaide University awarded him an honorary doctorate for service to society in 2008 and Flinders University bestowed an honour in 2011
- Mr Le will become governor of South Australia on September 2 this year
Mr Le worked as an accountant until he retired in 2009 and was made an Officer of the Order of Australia in 2010.
Mr Le says he is deeply honoured and humbled by the appointment.
"As a young boat people refugee, I arrived here 36 years ago with nothing but an invisible suitcase filled with dreams, [with] a dream to live in a peaceful, safe and free country and to live a meaningful and fulfilling life," he said.
"But to be bestowed with the greatest honour and the privilege of holding the vice-regal office is absolutely beyond my wildest dream.
"This appointment, however, says much more about our society than about me. It sends a powerful message affirming our inclusive and egalitarian society."
Cancer Council SA chief Brenda Wilson will succeed Mr Le as lieutenant-governor.
Mr Weatherill has thanked Rear Admiral Scarce for his work.
"His Excellency and Mrs Scarce have been outstanding advocates for South Australia in their roles," he said.
"I know many South Australians appreciate the contribution His Excellency has made as patron of more than 200 charities and organisations across the state.
"He has been tireless in his efforts to support the economic and social wellbeing of South Australians."