BRUSSELS—President Biden said Russia should be expelled from the Group of 20 major economies and pledged the U.S. would take in up to 100,000 refugees fleeing Ukraine as he met Thursday with world leaders to discuss new sanctions and humanitarian aid in response to Moscow’s invasion.

The gatherings in Brussels came amid concerns that Russian President Vladimir Putin could order the use of chemical or other unconventional weapons in Ukraine, a move Mr. Biden said would trigger a U.S. response.