A departure ceremony got underway at 11:00 a.m. Thursday at the Army Aviation Support Facility in New Castle.
The National Guard's 153rd Military Police Company is deploying for a 12-month tour.
"What they're going to be doing this time is training Afghan military and Afghan law enforcement" in security operations, said Del. National Guard Colonel Len Gratteri.
It was not the first deployment for many of the families attending Thursday's ceremony.
"It's our third time doing it together," Susan French of Wilmington told Action News, gesturing to her child, "but his first with a child so it's going to be a little bit harder."
Vice President Biden's wife, Jill attended Thursday's ceremony, along with other military officials.
127 men and women are going overseas with this unit, and 127 families are already looking forward to them coming back home.
"You keep yourself busy and make those Skype calls and do the best you can," said Susan French. "You all get through it."
After Thursday's ceremony the group headed to New Jersey's Joint Base McGuire-Dix-Lakehurst for training.
The group will spend four to six weeks at the base before heading to Afghanistan to relieve Montana's 44th Military Police Company.
The Associated Press contributed to this report.