Part of Project Sunrise, Qantas will operate 12 Airbus A350-1000s flights from Australia to other international cities such as New York and London.
These planes are expected to enter service by the end of 2025 from Sydney.
As part of Project Winton, the company will replace Boeing 737s and 717s with 20 Airbus A321XLRs and 20 A220-300s.
First flights under this project are anticipated to begin operations by the end of 2023.
The order also has an option to purchase another 94 aircraft, which can be delivered through 2034.
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Qantas Group CEO Alan Joyce said: “Throughout our history, the aircraft we’ve flown have defined the era we’re in. The 707 introduced the jet age, the 747 democratised travel and the A380 brought a completely new level of comfort.
“The A350 and Project Sunrise will make any city just one flight away from Australia. It’s the last frontier and the final fix for the tyranny of distance.
“As you’d expect, the cabin is being specially designed for maximum comfort in all classes for long-haul flying.”
Qantas’ A321XLR can accommodate 200 people, while the A220-300 has the capacity to accommodate 137 people.
Featuring Pratt & Whitney Geared Turbo Fan engines, both aircraft types are said to have 50% lower noise levels compared to the retiring 737 and 717 aircraft.
Last March, renewable fuels provider Aemetis signed an offtake agreement with Qantas Group and Qantas Airlines to supply sustainable aviation fuel (SAF).