Barry Gardiner said he would ask the Audit Office to investigate revelations by the BBC Spotlight programme about Invest NI's Belfast headquarters.
The Private Finance Initiative (PFI) was a way for the government to get buildings now and pay later.
But many contracts have been criticised as they turned out to be too expensive.
Invest Northern Ireland is a business development agency which aims to promote economic growth by providing government support to firms.
It signed a PFI contract for its new headquarters in Belfast in 2005.
After the property crash, it became a very bad deal.
Spotlight's research indicates that Invest NI's rent in 2012 was at least double the market rate and set a record for Belfast which still stands.
Invest NI has said that these are not valid comparisons, given the long-term nature of the projects.
Labour MP Mr Gardiner, who was Northern Ireland's direct rule enterprise minister when the 2005 contract was signed, said he will ask the Audit Office to investigate.
Tuesday's programme also reveals details of Invest NI's current multi-million pound debt to the controversial US investment fund, Cerberus.
Spotlight will be broadcast on BBC One Northern Ireland at 22: 40 BST on Tuesday, 20 June.

The Historical Institutional Abuse Inquiry is examining allegations of abuse in state-run children's homes and other institutions in Northern Ireland.
However, victims of clerical child abuse and former residents of Magdalene laundry-style institutions in Northern Ireland are excluded from the remit.
They have launched a joint campaign.
The two groups were due to call for the remit of the Historic Institutional Abuse Inquiry to be widened.
The inquiry, chaired by retired judge Sir Anthony Hart, was set up by the Stormont Executive and is examining cases from 1922 to 1995.
It will also determine if there were systemic failings by the state, or institutions, in their duties towards children under 18.
It was originally set up to investigate cases going back as far as 1945, but it was later extended to cover the period back to the foundation of the state in 1922.
Previously, Sir Anthony has opposed further extending the scope of his inquiry to deal with abuse which took place outside institutions.
He pointed out that such a move would have significant implications in terms of time and money.
The inquiry is currently investigating 35 residential facilities.
They include 15 state-run children's homes, 13 institutions run by Catholic Church orders and four borstals or training schools.
The inquiry was announced in December 2010 and the first phase began in October 2012.
Three institutions run by Protestant churches or voluntary organisations will also be investigated.

The aerodrome's owners had claimed that "permanent unrestricted planning permission" was granted in 1951.
However, this was rejected by Waverley Borough Council in July 2011 and the planning inspector in April 2012.
A judge at the High Court said the 1951 permission did not grant permission for unrestricted flying.
Lord Justice Sullivan said the permission for "flight testing" did not amount to consent for unrestricted flying of aircraft.
He said the certificate sought by the owners was pursued on the alleged basis that there was no material difference, in land use terms, between unrestricted numbers of passenger or cargo flights, and flight testing.
He said: "The use of land as a bus station is not the same thing as use of land for the testing of buses."
He added: "There can be no doubt that, properly construed, the 1951 planning permission does not permit the airfield to be used for unrestricted aviation activities."
Dunsfold Park was constructed during World War Two by the Canadian Army. It is now used by about 100 commercial operators and most famously as the venue for the filming of Top Gear.
The owners have the right to appeal the latest decision to the Supreme Court.
A Shadow Cabinet member and former Northern Ireland minister has called for an investigation into Invest NI's Private Finance Initiative contract.
[NEXT_CONCEPT]
Abuse victims whose cases are excluded from a Stormont inquiry into historical child abuse have united in a campaign for their allegations to be included.
[NEXT_CONCEPT]
The owners of Dunsfold Park aerodrome, which is home to the BBC's Top Gear, have lost their latest fight for unrestricted flying.