Addressing the European parliament in Strasbourg, Von der Leyen issued a rallying call intended to unite member states grappling with an energy crisis as winter draws near.
She described the Russian invasion as not only a war on Ukraine, but "a war on our economy, a war on our values and a war on our future".
Dressed in the blue and yellow colours of Ukraine's national flag, the commission president announced she would visit Kyiv later in the day and planned detailed discussions with its president, Volodymyr Zelenskiy, on ensuring Ukraine's "seamless access to the single market".
Ukraine's first lady, Olena Zelenska, was among the audience in Strasbourg and was given a standing ovation by MEPs.
Von der Leyen promised to work with Zelenska on the reconstruction of Ukrainian schools and pledged €100m (£87m) in EU funds. An estimated 70 schools have been damaged or totally destroyed by Russia.
The European Commission president, who has already visited Kyiv twice since the outbreak of war, also said the EU would stay the course with its sanctions on Russia. "The sanctions are here to stay," she said.
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