The agreement is due to come into effect in 2024, Anthony Albanese told reporters on Wednesday after a national cabinet meeting in Sydney.
In the March budget, the Morrison government pledged $12 billion over five years towards such an agreement designed to bring more consistency to funding for vocational education and training.
With national cabinet support, the Labor government will be able to start work on its own deal.
The lack of investment in TAFE and vocational education and training has been raised as an issue in the lead-up to the jobs summit, with unions and business groups joining forces to call for more funding for training organisations.
Australian Council of Trade Unions secretary Sally McManus and Business Council of Australia chief executive Jennifer Westacott have led the push for a streamlined enterprise bargaining system, with both saying they wanted to see workers' wages rise.
The prime minister welcomed the cooperation shown from businesses and unions at a BCA dinner on the eve of the summit, saying progress had already become evident.
"I'm sure there are people out there - perhaps even people in here - who see 'McManus and Westacott' as a somewhat unlikely double act," Mr Albanese said.
"But when we stop and think about it, it shouldn't be unusual."
Mr Albanese says unions, businesses and government all share the fundamental goals of growing the economy, boosting jobs, improving skills and lifting productivity.
"We agree on the destination: a strong growth, high productivity, fair wage future," he said.
"Given we agree on the destination, we can help each other on the journey to a better future."
The ACTU wants summit attendees to remember the real people affected by wage stagnation, poor conditions and cost of living pressures.
"It shouldn't be acceptable to anyone at the job summit that the profit share of national income is going up at the same time that the wages share is at historic lows," Ms McManus told reporters in Canberra.
"It's absolutely essential that we move forward with new collective bargaining models - it should be obvious to everyone that it is needed."
The final guest list for the much anticipated two-day summit includes 142 representatives from unions, community organisations, universities, government and business.
Among them is mining magnate Andrew Forrest, Atlassian boss Scott Farquhar and Qantas chief executive Alan Joyce.
As many as 28 union representatives have been invited, including participants from the ACTU, the Community and Public Sector Union and the Construction Forestry Maritime Mining and Energy Union.
Coles and Woolworths bosses also secured a spot, as did BHP and Rio Tinto chiefs.
Academics from several fields of expertise will attend, as well as representatives from clean energy groups, gender equality groups and disability rights advocacy organisations.
Deciding the final guest list was a difficult balance to strike, Treasurer Jim Chalmers said.
"The reality is you can't invite everyone that you would like ... we've got a good representative cross section of the Australian economy and community," he told reporters.
The Liberal Party will not be sending a representative.
Nationals leader David Littleproud, who has accepted an invitation, said worker shortages were more acute in the regions.
The summit would have a strong focus on the union movement, which would result in mass strikes, Opposition Leader Peter Dutton said.
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