The deal, agreed in June 2022 after four years of tough negotiations, is "ambitious", said European Commission President Ursula von der Leyen.
"It is a very well balanced free trade agreement," she added.
"New Zealand is a key partner for us in the Indo-Pacific region, and this free trade agreement will bring us even closer together," the EU chief said from Brussels.
New Zealand Prime Minister Chris Hipkins said it "will generate substantive new economic opportunities.
"It's of huge benefit to both partners," he said.
The EU is New Zealand's third biggest trading partner importing wines, fruit and meat into the continent.
Bilateral trade was just under nine billion euros ($9.9 billion) last year.
According to Brussels, EU exports to the South Pacific nation could increase by 4.5 billion euros a year. The bloc's investment in New Zealand could climb progressively by as much as 80 percent.
The deal includes a section on sustainable development, a first for an EU trade pact.
"For the very first time in a trade deal, we have included commitments on the Paris climate agreement," which set a goal of limiting global warming to well below two degrees Celsius, noted von der Leyen.
"With unprecedented social and climate commitments, it drives just and green growth while reinforcing Europe's economic security," she said.
To go into force, the agreement has to win the backing of the European Parliament and be ratified in New Zealand, where the economy fell into recession this year.
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