The 74-year-old will be laid to rest in a state funeral on Thursday at the Victorian capital's St Paul's Cathedral.
The Labor stalwart leaves behind devastated family and friends following his sudden death after exercising in Berlin last month.
The service will be live-streamed from 11am.
As ACTU vice-president, Mr Crean played a key role bringing about the Accord between unions and employers in 1983.
Elected to the Victorian seat of Hotham in 1990, Mr Crean became science minister in the Hawke government.
Narrowly missing out on the deputy leadership after Labor's election loss in 1996, he took on the position two years later after another election defeat.
After a third consecutive loss in November 2001 he was elected unopposed as leader.
Mark Latham was then narrowly elected leader over Kim Beazley, who challenged Mr Crean for the leadership in 2003.
Prime Minister Anthony Albanese will attend the service, along with former treasurer and Labor national president Wayne Swan.
Mr Albanese said the former Labor leader was one of the party's brightest figures.
"One of the things that I'm going to speak about today in my eulogy is his passion for the arts. He understood that this was a central part of Labor's mission - it wasn't something that was a decoration or an afterthought," Mr Albanese told ABC radio before the funeral.
"He understood that a culturally confident nation has the strength to know itself and ... has the imagination to enlarge itself and that's what he did with with his policy."
Acting Opposition Leader Sussan Ley will also pay her respects on behalf of the coalition.
"I remember Simon as being a good friend of rural and regional Australia. He was well respected in my electorate," she told ABC TV.
"I want to recognise a tough day for ... his family, for (wife) Carole, for the Labor Party more broadly."
After leaving politics, Mr Crean chaired the European Australian Business Council.
He is survived by his wife of 50 years Carole, daughters Sarah and Emma and grandchildren.
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