The orders allow authorities to seize assets over £50,000 ($86,000) from people suspected of corruption or links to organized crime until the owners account for how they were acquired.
A second, first-of-its-kind Unexplained Wealth Order was also filed in relation to her ownership of a $13.5 million golf course, purchased through a different company.
Jahangir Hajiyev is the former chairman of the International Bank of Azerbaijan.
Hajiyeva said in a witness statement that her husband was a man of substantial means.
Zamira Hajiyeva, the wife of a jailed banker from Azerbaijan, is being asked to explain her "unexplained wealth" thanks to a new anti-corruption enforcement scheme created to target organized crime figures and others with foreign government ties.
The "McMafia" suspect targeted by Britain's first unexplained wealth order can be identified today as the wife of an Azerbaijani state banker jailed for embezzling more than £100 million.
She unsuccessfully attempted to overturn one of the UWOs against an £11.5 million home in Knightsbridge and will now have to prove that the money used to pay for it was legitimately obtained. Judges also ordered him to repay $39m.
At an earlier court hearing, a lawyer for the NCA gave details of her spending at Harrods, a large chunk of it using 35 credit cards issued by her husband's bank.
"Unexplained Wealth Orders have the potential to significantly reduce the appeal of the United Kingdom as a destination for illicit income", Toon said.
Now a British court has demanded that Zamira Hajiyeva explain where she got her money from. Unless her appeal succeeds, she will have to explain further the source of the wealth used to pay for the home and the golf club just outside London.
Duncan Hames, director of policy at Transparency International UK, said the pressure group was "delighted" at the use of the Unexplained Wealth Order. Transparency International says it has identified £4.4 billion ($5.8 billion) in United Kingdom property bought with suspicious wealth, while other anticorruption campaigners have sought to highlight the problem by taking journalists on "kleptocracy tours" around London's swankiest streets.
During her unsuccessful challenge to the Unexplained Wealth Order, Mrs Hajiyeva said her husband was a legitimate businessman who had become independently wealthy thanks to a string of successful businesses, before becoming a chairman at the bank.
Last week, judge Michael Supperstone rejected Hajiyeva's appeal against the UWO although her lawyers said they would take the case to London's Court of Appeal.
"Unexplained wealth orders have the potential to significantly reduce the appeal of the United Kingdom as a destination for illicit income".
Investigators from the National Crime Agency believe there are billions of pounds of dirty money invested in British property - but it is nearly impossible to charge the owners with a crime or seize the assets because of a lack of evidence.