The first batch of the "Lightweight Multirole Missile (LMM)" systems -- made by French defence group Thales -- were set to be dispatched by the end of the year, the government said, as it bids to "speed up deliveries of aid".
The GBP 162-million ($213-million) package will be formally announced by Defence Secretary John Healey at a meeting Friday of Ukraine's Western allies in Germany.
"This new commitment will give an important boost to Ukraine's air defences and demonstrates our new government's commitment to stepping up support for Ukraine," he said in a statement.
"In recent days we have seen the tragic cost of Russia's indiscriminate strikes on Poltava and Lviv.
"These new UK-made missiles will support Ukraine to defend its people, infrastructure, and territory."
Healy took up the post in early July, after Labour replaced the Conservatives in power in the UK after 14 years in opposition.
The new missiles order comes days after he told Ukrainian counterpart Rustem Umerov that Britain would "ramp-up support over the coming months" during talks in London.
He confirmed that GBP 300 million worth of artillery ammunition will also start to arrive in Ukraine within months, according to the UK Ministry of Defence.
It said the latest missiles package was part of efforts to "step up UK and European defence production".
Thales, which builds the systems in its Belfast factory in Northern Ireland, describes the LMM on its website as "a lightweight, precision strike multi-role missile".
It is "designed to be fired from a variety of tactical platforms on land, sea and air against a wide range of conventional and asymmetric threats," according to the arms-maker.
The UK has already provided hundreds of LMMs to Ukraine for air defence, the ministry noted, adding they had been used to destroy Russian drones and other aerial threats.
Britain has been one of Kyiv's biggest backers in its fight against Russia's full-scale invasion, supplying long-range Storm Shadow cruise missiles and a squadron of 14 Challenger 2 tanks deployed early last year.
In a post on X last month, Zelensky praised the supply of lethal UK aid, noting it had saved thousands of lives, but added that "unfortunately, the situation has slowed down recently".
London promptly insisted its support remained "absolutely resolute".
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