Barry Sheerman, chairman of the education select committee, said he was concerned about the payments made by West London Academy, Ealing, and the King's Academy, Middlesbrough.
He said that the minister would be asked about the matter when he appeared before MPs next month.
"We believe that in public procurement certain procedures should be followed," he said. "All purchases should be competitively tendered for and there should not be a different set of rules for academies."
The TES revealed last week that West London Academy paid a total of pound;180,964 to businesses and a charity with major connections to its sponsor Alec Reed, the recruitment tycoon.
King's was billed for pound;290,214 by organisations and individuals connected to its sponsor Sir Peter Vardy, a Christian fundamentalist car dealer.
In a letter to The TES this week Mr Miliband said the payments were in line with Government accounting rules and procurement law and represented "best value for money" for taxpayers.
But last week's story established that none of the purchases were put out to competitive tender.
The Department for Education and Skills says that it is "good practice" for academies, like normal state schools, to obtain at least three tenders before purchasing goods and services. Independent watchdogs the Audit Commission and the National Audit Office are usually responsible for ensuring public money is spent economically, efficiently and effectively.
But an Audit Commission spokeswoman said this week that neither institution had any remit to investigate academies because the DfES had allowed them to appoint their own independent auditors. Academies are semi-independent, state-funded schools that form the centrepiece of the Government's plans to raise standards in secondary education.
Private sponsors, who can appoint a majority of the governors, contribute up to pound;2m towards their building costs, but running costs are met entirely by the taxpayer.
The Prime Minister wants to see 200 academies in development by the end of the decade.