Airbus said at a joint press conference in Paris it was the biggest single order for the widebody twin-engine aircraft from an airline, and would begin delivering the planes to the long-haul affiliate of the AirAsia group in 2015.
The order includes the latest version of the A330-300 capable of flying from Asia to Europe or the Americas non-stop.
"This order stamps our firm intent to dominate the long-haul, low-cost carrier space and marks the next phase in our development to be the undisputed global market leader," AirAsia X's director Tony Fernandes was quoted as saying in a statement.
AirAsia X is one of Airbus' biggest clients, with several hundred aircraft on order.
In June 2011 the Malaysian company ordered 200 A320 Neo planes with a catalogue price of USD 18.24 billion, one of the biggest ever orders of commercial aircraft.
It has also ordered 10 of Airbus' future long-range aircraft, the A350-XWB.
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