The federal government has finalised the panel, established by Prime Minister Tony Abbott, to be chaired by former Finance Department Secretary David Tune and head of the Remuneration Tribunal John Conde.
Former Speaker Harry Jenkins and former opposition leader Brendan Nelson will join the panel, as well as businesswoman Linda Nicholls, it was announced on Friday.
"The committee has the right mix of corporate knowledge, public sector administration and experience of the requirements and needs of elected representatives," Special Minister of State Michael Ronaldson said in a statement.
It will be a root and branch review, which will explore options to move to a simpler, transparent and independent system, he said.
The committee will provide its report in the first half of next year.
"I want this round of controversies to be not just the latest but the last," Mr Abbott told reporters in Tasmania.
The inquiry comes as federal Labor leader Bill Shorten backed his frontbench colleague Tony Burke, who has been criticised for his travel expense claims.
Mr Burke's taxpayer-funded travel record as a minister is under scrutiny after he led Labor's prosecution of Bronwyn Bishop travel claims that resulted in her resignation as Speaker.
He has admitted flying his children business class to Uluru, at taxpayer expense, in 2012 was beyond community expectations.
He also charged taxpayers $48,951 for a six-day trip in 2009, including first-class flights for a senior staffer, to attend a Barcelona food security forum as agriculture minister, The Australian said on Friday.
"Mr Burke's conduct has been within the rules at all times and he has my confidence," Mr Shorten told reporters in Sydney.
"I think it is important, though, that we now have a proper review of the rules, making sure they do accord with community expectations."
Cabinet minister Christopher Pyne said there was no point in taking pot-shots at individual cases of expenses.
"I don't see any great benefit of having a running commentary on MPs' entitlements," he told the Nine Network.
"If people stay within the rules, you can't then criticise them."
Mr Pyne's decision to fly his wife and four children business class from Adelaide to Canberra in 2013 has also been queried.
Federal Liberal MP Mal Brough published his taxpayer-funded travel expenses on his website on Friday and encouraged people to contact his office if they want to query them.
The member for Fisher has claimed $6618 for his travel this year and $2633 for his wife, who manages his Canberra office without any remuneration.
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