A total of 4,000 Nigerian citizens are still stranded in Ukraine.
In a statement on Twitter, the president's office said Ukrainian police and security personnel had reportedly refused to allow Nigerians to board buses and trains heading towards the Ukraine-Poland border.
"One group of Nigerian students having been repeatedly refused entry into Poland have concluded they have no choice but to travel again across Ukraine and attempt to exit the country via the border with Hungary," the statement said.
Mr Buhari's office said all foreign nationals trying to cross over to Poland to be "treated with dignity and without favour".
"All who flee a conflict situation have the same right to safe passage under UN Convention and the colour of their passport or their skin should make no difference," the statement said.
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