The King landed by helicopter at Blenheim Palace then mingled with world leaders including Ukrainian President Volodymyr Zelensky as well as Sir Keir Starmer.
King Charles III arrived at the Woodstock palace, the birthplace of Winston Churchill, mid-afternoon for the European Political Community summit.
More than 45 leaders gathered at the palace where Mr Zelensky called on delegates to show "collective will" against Russia following on from Vladimir Putin's invasion in February 2022.
During the summit, 44 countries and the EU agreed to target Russia’s “shadow fleet” of tankers seeking to evade sanctions on Russian oil.
The leaders were also set to attend a reception hosted by King Charles in the palace's Long Library, which has walls lined with more than 10,000 books.
READ MORE: Live coverage of European leaders gather at Blenheim Palace as police line streets
Earlier today, Sir Keir Starmer said he intends to “reset our relationship with Europe” as he hosted leaders from across the continent at a major summit.
The Prime Minister is using the European Political Community (EPC) gathering to push for closer security ties and joint action to tackle illegal migration.
The summit at Blenheim Palace in Oxfordshire comes as the new Labour Government attempts to forge closer links with the European Union (EU) after the turmoil of the Brexit years.
Sir Keir said: “European security is at the forefront of my Government’s foreign and defence priorities.
“We will only be able to secure our borders, drive economic growth and defend our democracies if we work together.
“It’s time to reset our relationship with Europe.”
Sir Keir personally greeted leaders as they arrived at the 18th century palace.
As part of the drive to tackle illegal migration the Government has redeployed more than 100 Home Office staff from working on the now-scrapped Rwanda scheme to focus on a “rapid returns unit” to send people with no right to be in the UK back to their home country.
The Prime Minister called for continent-wide action to tackle the international “people-smuggling webs”.
Flanked by Volodymyr Zelensky during the opening of the summit, the Prime Minister said the first task of the European Political Community (EPC) is to “confirm our steadfast support for Ukraine”.
“Every day Ukraine fights affects not just the Ukrainian people, but the European people,” he said.
“A continent where our belief in freedom, democracy and the rule of law was hard won and that wants to live in peace.”
Mr Zelensky said he would “sign an intergovernmental agreement with the UK on support for the Ukrainian defence and industrial complex, discuss future defence co-operation, and expand our defence capabilities”.
“Since the first days of the full-scale invasion, the UK has been one step ahead in its determination to support Ukraine. This is the kind of resolve we need to stop Russian terror,” he said.
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