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.
A Shadow Cabinet member and former Northern Ireland minister has called for an investigation into Invest NI's Private Finance Initiative contract.