The aircraft, a revamped and more fuel-efficient version of the A330 with new Rolls-Royce (>> Rolls-Royce Holding PLC) Trent 7000 engines, is due to enter service in late 2017.
TAP ordered 14 of the jets as part of a wider fleet reorganisation last year.
The Portuguese airline will also be the first to take a new cabin layout called "Airspace," being showcased at an industry event in Hamburg this week.
The design allows airlines to add more seats, Airbus said last month.
Airbus (>> Airbus Group) launched the 250-300-seat A330neo in 2014 partly to plug a gap left by disappointing sales of the smallest version of its newer A350 series.
(Reporting by Tim Hepher; Editing by Mark Potter)