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“It is an avalanche of people with cars, with pets,” Mr. Grandi said. “It’s entire cities being emptied, and crossing the border.”

Poland has taken in the largest number of Ukrainians, but Mr. Grandi was particularly concerned about Moldova, which has received more refugees per capita than any of Ukraine’s other neighbors. Since Feb. 24, more than 200,000 people coming from Ukraine have entered Moldova, which is home to 2.6 million and is one of Europe’s poorest countries.

Unlike its neighbors to the west, Moldova is not a member of the European Union, and therefore lacks significant institutional support from the bloc.

Russia on Saturday appeared to ratchet up diplomatic tensions with the United States, announcing it had detained the American basketball star Brittney Griner as she tried to leave the country from Moscow’s airport last month. The Russian authorities said they found vape cartridges with hashish oil in her luggage, a claim that could not be independently verified.

Over the past week, the United States, Europe and others have frozen hundreds of billions of dollars of Russian assets, removed Russian banks from a system that enables international payments, and erected steep barriers to investment in Russia. Businesses are pulling out at an ever accelerating pace, the Moscow stock market has yet to reopen, the ruble plunged to a low and residents face the prospect of severe shortages.

Visa Inc. and Mastercard on Saturday became the latest Western companies to announce the suspension of their Russian operations, severely curtailing the ability of millions of Russians to make payments at home and abroad.