Mitchell was charged with Promoting Prison Contraband 1st Degree, and Criminal Facilitation, 4th Degree, both felonies.
This as squads of law enforcement officers spent a seventh day searching for the two murderers who escaped from the maximum-security prison in northern New York.
Armed officers in body armor, they started boarding New York state prison system buses soon after dawn Friday in the village of Dannemora, where David Sweat and Richard Matt used power tools to cut their way out of their neighboring cells last weekend. They remain at large.
The hundreds of state, federal and local officers conducting the search spent Thursday slogging through a swampy patch of woods just east of Dannemora after investigators had received tips that the convicts were in the area.
State Route 374, the main road leading into Dannemora, remains closed for a second day, as does the local school district.
The rugged northern New York terrain being searched for two escaped murderers presents major challenges to anyone who ventures into the Adirondack woods.
Experts say if Sweat and Matt are in the wooded, swampy area just east of Clinton Correctional Facility in Dannemora, they're enduring two of the region's warm-weather nuisances: swarms of biting insects.
Curt Stager, a biology professor at Paul Smith's College in the Adirondacks, tells the Press-Republican of Plattsburgh that black flies come out during the day while mosquitoes are just as prevalent at night.
There has been no confirmed physical sighting of either man. At a news conference outside the maximum-security prison on Wednesday, New York State Police Superintendent Joseph D'Amico said, "I have no information on where they are or what they're doing, to be honest with you."
"She befriended the inmates and she may have had some role in assisting them, but I'm not going to go into any further details," D'Amico said prior to Mitchell's arrest.
Two sources said that Mitchell, a supervisor at the Clinton Correctional Facility tailor shop, was quizzed within the past year over an alleged relationship with David Sweat, one of the two escapees who broke out of the lockup in Dannemora in a plot straight out of "Shawshank Redemption."
On Thursday, Gov. Andrew Cuomo said that investigators had received tips that the convicts were in the area, and that tracking dogs had picked up the scent Thursday morning.
"We had tips yesterday they were in Vermont. We have tips today that they're in the immediate area so you just follow every tip and we don't have any hard information one way or the other," said Cuomo. "We're following every tip, that's all I can say. Look - They could either be 4 miles from the prison or they could be in Mexico, you just don't know."
But authorities expanded the search after investigators learned that the inmates had talked before last weekend's breakout about going to neighboring Vermont.
"We have information that suggests they thought New York was going to be hot. Vermont would be cooler, in terms of law enforcement," Vermont Gov. Peter Shumlin said at the news conference with New York Gov. Andrew Cuomo.
Shumlin and other officials would not say how authorities learned that information.
Vermont authorities are patrolling Lake Champlain and areas alongside it, Shumlin said. Cuomo urged the people of Vermont to be on the alert and report anything suspicious, warning: "Trust me, these men are nothing to be trifled with."
Former FBI executive and ABC News security consultant Steve Gomez ran through some of the advantages and pitfalls of where the men might have gone in a story featured on ABCNews.com.
The killers' mugshots have been put on more than 50 digital billboards in New York, New Jersey, Massachusetts and Pennsylvania, police said, and a $100,000 reward has been posted.
The Associated Press and ABC News contributed to this report.
Law enforcement officials again asked the public to report anything out of the ordinary null