Second only to President Xi Jinping in China's political hierarchy, Li is the most senior figure to arrive on official business in either nation since 2017.
Over six days, Li will set foot in five different cities, meet two prime ministers, hold talks with a string of business leaders, and engage in China's trademark "Panda diplomacy".
A noisy crowd greeted Li as his motorcade pulled into the Intercontinental Hotel in the heart of New Zealand's capital Wellington.
Cheering supporters banged drums and waved banners, while a smaller group of shouting protesters clambered to get a look at his car.
Shortly after touching down, Li issued a statement highlighting the "fruitful outcomes" that flowed from doing business with China.
Li said he was aiming to renew China's "traditional friendship" with New Zealand, hinting at opportunities to bolster trade, tourism and investment.
China's relationship with both hosts has shifted drastically in the seven years since Li's predecessor toured Down Under.
New Zealand, long seen as one of China's closest partners in the region, has become increasingly bold in its criticism of Beijing's role in the South Pacific.
Meanwhile, Australia has grown closer to the United States in response to China's expanding military might.
But there remains one constant: China is still, by far, Australia and New Zealand's largest export market.
- Don't risk it -
Geopolitical analyst Geoffrey Miller told AFP that Li's visit carried a not-so-subtle message: "Don't put it all at risk."
New Zealand has been mulling whether to play a limited role in the AUKUS security pact between Washington, London and Canberra -- a pact seen as key to countering China's military expansion.
At the same time, Foreign Minister Winston Peters has called out China's attempts to bolster its security footprint in the Pacific Islands.
Miller, from Wellington's Victoria University, said Li would dangle trade "carrots" in an attempt to soften this stance.
Beijing was likely to offer incentives to show New Zealand "what it could lose" if it agrees to join AUKUS in developing defence technology, he said.
"China is aware that no final decision has been made. So there is the chance to impress upon New Zealand the weight of that decision."
New Zealand was one of the first developed nations to ink a free trade deal with Beijing, and today almost a full third of its goods exports are shipped to China.
Chinese consumers have a voracious appetite, in particular, for New Zealand's premium meat, dairy and wine.
- Panda diplomacy -
Li will fly out of New Zealand's commercial hub Auckland on Saturday morning, bound for the southern Australian city of Adelaide.
Sitting on the doorstep of the famed Barossa winemaking region, Adelaide is the hometown of Foreign Minister Penny Wong, who is credited with helping stabilise relations between Canberra and Beijing.
Australian wine was among a slew of commodities effectively barred from China at the height of a rancorous and years-long trade dispute that only recently started to subside.
While wine, coal, timber, barley and beef exports have largely resumed, trade barriers remain for Australian rock lobster.
One of Li's first stops will be Adelaide Zoo, widely seen as a sign that giant pandas Wang Wang and Fu Ni, who have been loaned there from China since 2009, will be extending their stay abroad.
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