Ukraine’s state-run railway company Ukrzaliznytsya said it is not yet known if there are any casualties.
It added that the building suffered minor damage but trains are still operating.
Ukrainian interior ministry adviser Anton Herashchenko said the blast may have cut off central heating supply to parts of the capital.
Katerina Sergatskova, editor of the Kyiv-based Zaborona media outlet, tweeted: “Russian rocket hits the main Kyiv railway station where hundreds of people stay overnight with children waiting for the next evac train.
“How many people were injured is unknown so far.
“How far are Russians from ISIS?”
It comes on the seventh day of Vladimir Putin’s invasion of Ukraine.
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