Mayor Vincent Gray's office issued the order in response to the muggings of participants of the program. Last year, at least five participants -- some of whom were wearing shirts with the program's name on them -- reportedly were mugged on paydays.
Deputy Mayor for Public Safety Paul Quander said that the deployment began three weeks ago.
"We wanted to use our resources wisely and strategically," he told the newspaper. "We are not putting (firefighters) at any additional risk. I think it enhances their ability to connect with the community."
D.C. Fire and EMS spokesman Lon Walls told the newspaper that the firefighters are not expected to act as law enforcement officers.
"Sometimes a uniform presence can be a deterrent," he said.
Quander said that if criminal activity takes place, the firefighters will not take action and will instead radio for police.
Some worry though that placing the firefighters on the city's worst blocks for crime will put them at risk.
"I'm concerned that this is a knee-jerk reaction to what is a serious problem that is clearly a police matter and not a fire department matter," fire union President Edward Smith said.
Police union Chairman Kristopher Baumann echoed Smith sentiment.
"They are going to send unarmed, untrained firefighters out into some of the most dangerous areas."
A police department e-mail obtained by the newspaper shows that the firefighters will be stationed at 14 spots across the city, sometimes as late as 4 a.m.
Wednesday was the first payday for the more than 14,000 14- to 21-year-olds who take part in the program.
One participant was mugged that morning and during the first week of the program, two female participants reported sexual assaults at their job sites, Quander told the newspaper.