The 27-nation EU has so far trained over 80,000 Ukrainian soldiers outside the borders of the war-torn country to help it battle Moscow's invasion.
Kallas said the move could be part of broader Western security guarantees given to Ukraine to help shore up any ceasefire agreed with Russian President Vladimir Putin.
"I welcome that there is broad support today to expand our EU military mission mandate to provide training and advice inside Ukraine after any truce," Kallas said after talks with EU defence ministers.
"We must be ready to do more. This could include placing EU trainers in Ukrainian military academies and institutions," she said.
As part of the US-led peace efforts, Western powers are discussing how to guarantee Ukraine's security in case of a truce deal.
President Donald Trump has indicated the United States could play a role backing up a European peacekeeping plan, but would not deploy American soldiers to Ukraine.
Despite Trump throwing his weight into trying to end the war, Moscow continues to stall on a potential meeting between Russian President Vladimir Putin and Ukraine's Volodymyr Zelensky.
In the meantime Moscow has carried out waves of bombardments on Ukraine, including deadly strikes on Kyiv this week.
"The past weeks we have seen diplomatic efforts to end Russia's war, and it's clear that Europe wants peace. America wants peace. Ukraine wants peace," Kallas said.
"Who doesn't want peace is Russia."
Putin defends Ukraine invasion at China summit, blames West
Tianjin, China (AFP) Sept 1, 2025 -
Russian President Vladimir Putin sought on Monday to defend his Ukraine offensive to Moscow's allies, blaming the West for triggering the three-and-a-half year war that has killed tens of thousands and devastated much of eastern Ukraine.
"This crisis was not triggered by Russia's attack on Ukraine, but was a result of a coup in Ukraine, which was supported and provoked by the West," Putin said at a summit of the the Shanghai Cooperation Organisation in the Chinese city of Tianjin.
That is a reference to Ukraine's 2013-2014 pro-European revolution, which ousted a pro-Russian president.
Moscow responded by annexing the Crimean peninsula and backing pro-Russian separatists in the east, triggering a civil war.
"The second reason for the crisis is the West's constant attempts to drag Ukraine into NATO," the Russian president added.
Putin was speaking at the SCO summit, attended by Russian allies, including Chinese President Xi Jinping, Indian Prime Minister Narendra Modi and Iranian President Masoud Pezeshkian.
Moscow and Beijing have touted the Shanghai Cooperation Organisation as an alternative to Western-led political and security blocs, including NATO.
Putin said the world needed a "system that would replace outdated Eurocentric and Euro-Atlantic models, and take into account the interests of the widest circle of countries".
"We highly value the efforts and proposals of China, India and our other strategic partners, aimed at contributing to resolving the Ukrainian crisis," he added.
Despite US President Donald Trump urging both Moscow and Kyiv to strike an agreement to end the war, peace proposals have stuttered.
Putin has rejected calls for a ceasefire and tabled hardline territorial and political demands -- calling for Ukraine to cede more territory and renounce Western backing -- as preconditions for peace.
Kyiv has ruled them out as non-starters.
The Russian leader said he would discuss the diplomacy to end the conflict and his latest talks with Trump in a series of bilateral meetings.
He is set to meet Modi, Pezeshkian and Turkey's Recep Tayyip Erdogan for separate talks later Monday.
Putin meets Erdogan, praises Turkey's mediation efforts on Ukraine
Tianjin, China (AFP) Sept 1, 2025 -
Russian President Vladimir Putin praised Turkey's mediation attempts around the Ukraine war at a meeting with his Turkish counterpart Recep Tayyip Erdogan in China on Monday.
"I'm confident that Turkey's special role in these matters will continue to be in demand," the Russian president said during talks with Erdogan on the sidelines of the Shanghai Cooperation Organisation (SCO) summit.
Putin added that the three rounds of direct talks with Ukraine in Istanbul have made some progress on the humanitarian track.
The talks have failed to yield a breakthrough over Russia's three-and-a-half-year invasion and resulted only in exchanges of prisoners and soldiers' bodies.
The warring sides have radically different positions and Ukraine has accused Russia of sending low-level officials with no real decision-making power to the Istanbul talks.
Russia has called on Ukraine to effectively cede four regions that Moscow claims to have annexed, a demand Kyiv has called unacceptable.
US President Donald Trump has called for a meeting between Putin and Ukrainian President Volodymyr Zelensky, but Moscow said it was too early to do so before key issues are resolved.
Russia's full-scale invasion, launched in February 2022, has ravaged swathes of eastern and southern Ukraine, killing tens of thousands of soldiers and civilians.
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