The megabank's global headquarters in Tribeca were briefly shut down as activists blocked employees from getting into work.
The crowd was part of ongoing protests during Climate Week and marked the second day of climate protests in Manhattan.
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Officials say protesters unfurled a large banner outside of the building on Greenwich Street starting at 8:30 a.m.
The activists who demonstrated Thursday morning said their message was sent about the dangers posed by global climate change. They claim corporations are making the problem worse.
Activists say Citi is one of the largest funders of the fossil fuel industry in the world and protesters believe the company profits from the climate crisis.
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Most of the arrests made are expected to be disorderly conduct, which will be desk appearance tickets or summonses.
On Wednesday a similar protest at Blackrock led to five arrests in Midtown Manhatten.
The protest comes as the U.N. prepares to hold a climate summit next week.