Two interns at discovered the substance when they opened the letter at the Democratic presidential candidate's Manhattan office at 5pm, the New York Post reports.
The staffers then took the letter to Clinton's campaign office in Brooklyn at around 5.30pm - exposing another two people.
It was not yet clear if the substance was dangerous.
But authorities there are fears it could be toxic after the infamous anthrax attacks in 2001 that followed September 11.
During that year, powdered anthrax was mailed to several news media offices and members of congress, killing five people and infecting 17 others.
Clinton was not in New York at the time of the evacuation.
The former first lady was at a community college in Cleveland, Ohio, as part of a multi-day campaign trail tour of the swing states.
This appears to be the first time that anyone has targeted Clinton or her campaign in this way.
But her Republican rival Donald Trump and his family have received several suspicious substances in the post in the past year - although all turned out to be non-toxic.
Emergency crews were called out to Trump Tower in August after the discovery of a suspicious substance in a subcellar of the Upper East Side building.
No-one was injured in the scare.
The last time anyone sent a suspicious package to the Clintons was a decade ago when a letter full of white powder was sent to former President Bill Clinton’s Harlem office in 2006.
The substance was later found to be nontoxic, but its discovery led the authorities to evacuate two floors of the building.
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